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Vapour Pressure Measurement in the Storage and Transport of Crude

Oil
Paper # 2015-0268
Bob Birchmore
Icon Scientific Ltd
Bath
United Kingdom

The measurement and control of vapour pressure is important in the storage and transport of
crude oil. However, vapour pressure measurement and its relevance are often a cause of
confusion. This paper will provide a definition of what vapour pressure is, why it is important
and discuss terms such as Reid Vapour Pressure, True Vapour Pressure and the ASTM
vapour pressure test methods.
What is vapour pressure?
Vapour pressure is a measure of volatility (the tendency of a substance to pass into the
vapour state). Products with higher vapour pressures are more volatile than products with
lower vapour pressures. With hydrocarbon products, vapour pressure limitations are often
applied to prevent pump cavitation during product transfer and pressure build up during
storage. Vapour pressure is an important property for motor gasoline with a direct effect on
cold starting and driveability. It can also be used as a measure of potential hydrocarbon
emissions to atmosphere and be subject to environmental regulation.
The vapour pressure of a liquid is defined as the pressure exerted by the molecules that
escape from the liquid to form a separate vapour phase above the liquid surface.
For a liquid to evaporate under any set of conditions, molecules must escape from its
surface. Molecules are constantly moving, the speed of a molecule depends upon its
temperature and mass. That is, for any given input of energy (temperature) lighter molecules
will move faster than heavier ones and will be more likely to gain enough speed to leave the
liquid surface and become a vapour.
To illustrate the above, imagine a closed vessel at constant temperature that has an open
container of a volatile liquid placed inside it (fig1). If the temperature conditions are right
some molecules will gain enough energy to escape the liquid surface. As the molecules
continue to escape they collide with the sides of the vessel and lose energy (speed) and
some even return back to the liquid. The collision of billions and billions of molecules against
the vessel sides develops a pressure, this is the vapour pressure. Eventually, at a given
temperature, the number of molecules leaving the liquid equals the number of molecules
returning to the liquid (fig 2). When this happens the system is at equilibrium. The pressure
inside the vessel will be the equilibrium vapour pressure. If the temperature is then raised,
more molecules will escape, until a new equilibrium is reached. There are now more
molecules in the vapour space and the equilibrium vapour pressure will rise (fig 3). If the
vessel is now opened the molecules escape into the atmosphere. There will be no
measurable pressure in the vessel, the molecules will now be vainly trying to establish an
equilibrium with the atmosphere and the liquid will eventually evaporate away completely.

Fig 1

Fig 2

Fig 3

Fig 4

Vapour Pressure Units


Vapour pressure may be expressed in any convenient pressure units. In scientific
applications the preferred unit is mostly millimetres of Mercury (mmHg). In Europe petroleum
vapour pressure is normally expressed in Pascals (as the Pascal is a small unit of pressure
the pressure is normally expressed in KiloPascals (kPa)). Outside of Europe and in the USA
the preferred unit is pounds per square inch (psi).
1 kPa = 0.145psi = 7.60 mmHg
For most purposes vapour pressure is expressed as an absolute pressure
Absolute pressure and gauge pressure
These terms can be confusing. The word absolute is another term for real, genuine or
actual. Absolute pressure is referenced to zero pressure (a vacuum). Gauge pressure is
referenced to atmospheric pressure. An absolute pressure gauge connected to atmosphere
would register 14.7 psia, while a gauge pressure gauge would register 0 psig.
Vapour Pressure Variation with temperature.
Vapour pressure increases in a non-linear way so that the logarithm of the vapour pressure
is proportional to the reciprocal of the absolute temperature. Consider water as a familiar
example its vapour pressure temperature graph is shown in fig 5 and a plot of its log vapour
pressure Vs the reciprocal of absolute temperature is shown in fig 6

Fig 5

Fig 6

When the vapour pressure of a liquid is equal to the applied pressure (atmospheric pressure
in this case) bubbles of vapour form in the liquid i.e it is boiling. With water this happens at

100C. If water is heated in closed vessel like a boiler, the vapour cannot escape so the
boiling point increases and the pressure and temperature build up, so steam supplied at a
pressure of 2 atmospheres (1500mm Hg) will be at a temperature of 120C not 100C. We
can equally say that at 1500mm Hg absolute (760mm Hg gauge, 14.7 psig 100kPag) water
has a boiling point of 120C. If the pressure is reduced the boiling point is also reduced
(remember that a liquid will boil when its vapour pressure is equal to the applied pressure.)
This is exploited in vacuum distillation to lower the boiling point of substances below their
decomposition points and reduce energy consumption).
Atmospheric pressure reduces with height. As an example, at the top of Mt. Everest where
the atmospheric pressure is much less (about 60% of that at sea level or about 460mm Hg)
water would boil when its vapour pressure rises to 460mm. From fig 5 we can see this will be
about 70C (72C in fact). It is often stated that typically the rate of a chemical reaction
doubles for every 10C rise in temperature. If boiling an egg is considered a chemical
reaction, this takes 6 minutes at ground level. On top of Everest it would take 336 minutes or
about two and a half hours.
A substance that is liquid normal temperatures and pressures will have a vapour pressure
below 14.7 psia (i.e. it will not be boiling). For example, most motor gasolines and stabilised
crude oils have vapour pressures of around 10-12 Psia at 100F (37.8C). Very light
products such as liquefied petroleum gas (LPG) will have much higher vapour pressures at
around 170-180 Psia.
Partial Pressure
This is another term associated with vapour pressure. The air is pressing down on us giving
rise to an atmospheric pressure of 14.7 pounds per square inch at sea level. In an open
vessel volatile molecules will be escaping (evaporating) into the air. The amount of
molecules escaping is not sufficient in any way to increase the atmospheric pressure of the
whole of the Earths atmosphere so the atmospheric pressure remains the same. A dish of
water open to the air is still developing a vapour pressure. So if the water is at 50C it will
have a vapour pressure of 92.5 mm (see Fig 5). This means that at the liquid surface where
the water is in equilibrium with the surrounding air the total pressure will still be 760mm but
92.5mm of it will now be due to water vapour. So the water content of water saturated air at
50C at sea level is 92.5/760 x 100 = 12.17%.
If the water were at 0C its vapour pressure would be 4.6mm so the air above it would now
contain 0.6% of water. So the partial pressure of water is 92.5mm at 50C and 4.6mm at 0C
Vapour Pressure of mixtures (Raoults Law)
So far we have only considered a single component(water). Raoult (1882) formulated a law
governing the vapour pressure of ideal mixtures. It states that the partial (vapour) pressure
of each component in an ideal mixture of liquids is equal to the vapour pressure of the pure
component multiplied by its mole fraction (concentration) in the mixture. So each component
behaves like the others are not there (ideal behaviour) and contributes towards the total
vapour pressure at a particular temperature according to its vapour pressure at that
temperature and its concentration in the mixture.

How vapour pressure is measured in the oil industry


For Petroleum products the ASTM and other bodies lay down a number of standard vapour
pressure test methods. We have seen above, that theoretically if the concentration and
vapour pressure of every component in a mixture is known, the vapour pressure may be
calculated. However, for crude oil and other petroleum products, this is impossible due to the
hundreds and thousands of individual components present.
In simple cases such as mixtures of relatively few compounds whose properties are well
known such as LPG, there is a compositional analysis method ASTM D2598 - 12 Standard
Practice for Calculation of Certain Physical Properties of Liquefied Petroleum (LP) Gases
from Compositional Analysis. This is based on the analysis of 16 compounds from C1 to C6
that are typically found in LPG.. Vapour pressure is one of the properties calculated using
Raoults law. All other vapour pressure test methods use an empirical pressure
measurement of some sort, based on a standard apparatus and procedure.
ASTM D323 Reid Vapour pressure aka RVP.
This is a very early standard vapour pressure test method. It was devised in the 1920s by a
Dr Reid, apparently as a result of a contest to come up with a practical way of testing vapour
pressure on natural gasolines (the method was later extended for other products as well).
The method is well established and remains the reference for many products.
Summary of the method.

The Reid vapour pressure apparatus consists of a chilled liquid


chamber (0-1C) that is screwed onto a vapour chamber fitted
with a pressure gauge. The liquid chamber of the vapour
pressure apparatus is filled with the chilled, air-saturated
sample,(0-1C) and connected to the vapour chamber that has
been heated to 37.8 C (100 F) by immersion in a temperature
controlled water bath. The whole assembled apparatus is then
immersed in the bath and gently shaken until a constant
pressure reading is observed. The reading is reported as the
Reid vapour pressure. The nominal vapour/liquid ratio during the
test is required to be 4:1 (ie the volume of the vapour chamber is
4 times the volume of the liquid chamber (the reason for this
ratio is not clear).
Fig 7
Additional points Concerning ASTM D323.
1) This method was also adapted for vapour pressure measurements of LPG as ASTM
D1267.
2) The sample is cooled to prevent loss of volatile (high vapour pressure) components
but the sample is exposed to the air during the test procedure so very volatile
components can be lost. (The Reid vapour pressure is really the difference in vapour
pressure of the sample at 0-1C and the vapour pressure of the sample at 37.8C). It

is measured with a gauge pressure gauge but the pressure registered is a difference
so is an absolute value.
3) As the dissolved air content of the product was not known and dissolved air could
contribute to the vapour pressure the cooled sample was shaken with air to saturate
it so that all samples started the test with nominally the same amount of dissolved air.
This is another opportunity to lose volatile material.
4) The method is a manual one and requires a degree of skill to carry out. There is no
automated D323 apparatus.
Many petroleum products have an RVP specification associated with them. It must always
be remembered that:1) RVP is only RVP if measured at a 4:1 vapour liquid ratio at 37.8C (100F) using the
RVP apparatus and procedure.
2) Vapour pressure measured at different ratios or temperatures from D323 is not RVP.
3) Vapour pressure measured by any other test method/apparatus cannot be called
RVP it may be corrected to an RVP value which can be termed RVP equivalent (RVPE).
4) RVP is not True Vapour Pressure (TVP).
ASTM D4953 aka Dry Vapour Pressure (DVP)
In the 1970s refiners started to use oxygenated compounds in gasoline like Ethanol and
MTBE this gave problems with the ASTM D323 RVP test. The problem was that oxygenates
are water soluble and they dissolved in the water traces left in the D323 apparatus after
cooling. This led to lower vapour pressure results than expected. To get around this the
D323 method was revised. The procedure remained very similar except that a dry cooled
apparatus was used. So the results of this test are normally referred to as Dry Vapour
Pressure (DVP) or sometimes as Dry Reid Vapour Pressure (DRVP). RVP specifications
have now been dropped for spark ignition fuels as they all contain oxygenates and DVP (see
later) remains the vapour pressure result that most gasoline producers would be interested
in (although it is still erroneously referred to as RVP in some cases).
ASTM D5190, D5191, D5482, D6377 and D6378 etc.
The problem with ASTM D323 and D4953 were that they were still manual test methods with
plenty of scope for losing volatiles and human error. As a result of this there were various
other automatic or semi-automatic methods introduced from the 1970s onwards to try to
simplify and improve things. The problem was that products continued (and still continue in
many cases) to be specified in terms of ASTM D323 and D4953.
This meant that a lot of work went into establishing the bias between the vapour pressure as
measured by these convenient new tests and the vapour pressure measured by the old
methods. So while all these newer tests produce a vapour pressure result in their own right
the results are nearly always converted to an ASTM D323 or ASTM D4953 equivalent result
by means of a conversion factor given in the method. The results so obtained are called
Reid Vapour Pressure Equivalent (RVPE) or Dry Vapour Pressure Equivalent (DVPE) or
Dry Reid Vapour Pressure Equivalent (DRVPE).
These automatic methods either inject a small amount of sample (1 volume) into a larger
vessel (4 volumes) at atmospheric pressure, or into a similar vessel held under vacuum

(very similar to the example we considered earlier) and the rise in pressure is measured by a
suitable transducer. In general the vacuum methods were preferred as equilibrium was
faster to achieve reducing the measurement time. The problem was that a vacuum pump of
some sort was needed. This was worked around in the latest expansion methods in which
the measuring chamber is fitted with a moveable piston that incorporates a pressure
transducer. The sample is held under the piston, the temperature is stabilised and then the
piston moved out to the desired V:L ratio. Once equilibrium is reached the transducer then
reads the vapour pressure. Now the Vapour pressure tests are automated is now possible to
design online analysers that can duplicate the laboratory test methods.

It is now rare for any laboratory to be carrying out the old D323 and D4953 methods, they
will be most likely be using some form of automatic analysis and correlating.

A summary of current vapour pressure methods is given in appendix:1.


Crude Oil
Most crude oils require to be degassed (stabilised) to regulate their vapour
pressures before they are transported or stored to prevent potential boiling and
pressure build up to levels that can cause loss of vapour to the air or damage to
tanks, or damage to pumps due to cavitation (vapour forming in the liquid at pump
suction). Typically the vapour pressure was (is) regulated to an RVP (at 100F) of
around 10psia.
However, this only represents the situation at 100F. Crude oil may well be stored at
temperatures above 100F. In which case, the vapour pressure and the potential
pressure in the storage vessel will rise.
To overcome this, the API produced a nomogram to determine True Vapour
Pressure (TVP) to convert RVP to a TVP value at a higher temperature. This
nomogram is based one crude oil, and has been found to be inadequate in many
cases and crude oils regulated to an RVP value can develop much higher
unexpected pressures during storage and transport.

Fig 9 Estimation of API TVP from RVP data


(source API manual of Petroleum
Measurement Standards (formerly API
publications 2517&2519 Evaporative loss
measurement

True Vapour Pressure (TVP)


There is confusion over what constitutes True Vapour Pressure. What is true, is that
RVP/DVP or any of the equivalent methods do not actually measure TVP and that there is
no ASTM standard test method to determine TVP on mixed composition samples.
If the RVP of a pure liquid is measured at a specific temperature the result obtained will be
the true vapour pressure of the liquid. This is because there is only one type of molecule
present in the vapour.
Petroleum products are multi-component. They will potentially contain small amounts of very
volatile components with very high vapour pressures (methane, ethane etc.). The key here is
the words very small amounts If the vapour pressure is measured at the 4:1 ratio of the
RVP test, the small amounts of these very high vapour pressure components will turn
straight into high pressure vapour but the amount of vapour generated may be so small
that it does not overly affect the lower pressure generated by the vapour from the
overwhelming concentration of less volatile components that form the bulk of the sample.
This is especially true in the case of crude oil and crude oil condensates.
Essentially RVP and API TVP data only applies to storage tanks that are 20% full at 100F.
Normally tanks are filled to 98% capacity. So the V:L ratio is 0.02:1 not 4:1. A high pressure
can form in the small 2% ullage space due to out-gassing of the small amount of very high
vapour pressure hydrocarbons present.
To gain a knowledge of the real maximum pressures that can build up in storage we need to
reduce the vapour space to a theoretical zero and measure vapour pressure at a 0:1
vapour:liquid ratio. This in reality is the True Vapour Pressure. For practical use True Vapour
Pressure should ideally be measured at the actual temperature of the sample or the
maximum storage temperature, if this is likely to be more than 100F.

TVP Measurement
In practice it has proved impossible to measure at a 0:1 vapour:liquid ratio with the new
expansion methods so indirect methods are used. To overcome the limitations of RVP

and API TVP, ASTM method D6377 Standard Test Method for Determination of
Vapor Pressure of Crude Oil: VPCRx (Expansion Method) has been introduced and
is widely gaining acceptance.
The x in the D 6377 method title refers to the V:L ratio employed during the test.
D6377 allows measurement at RVP (x = 4) conditions and a conversion factor to
obtain an RVP equivalent result is given in the method. The method recognises that
Vapor pressure of crude oil at various V/Ls is an important physical property for
shipping and storage and that measuring at a V:L of 0.02 closely mimics the
situation of an oil tanker(2% ullage space). While this measurement is not referred
to as TVP in the method the implication is that a 0.02:1 measurement is much closer
to actual TVP than RVP or API TVP. The method also mentions that the
measurement of vapour pressure at a whole range of temperatures and V:L ratios
can be useful (it would for example permit the user to construct their own version of
the API TVP nomogram based on their particular crude).
Working at an expansion ratio of 0.02 has given problems with repeatability. Firstly,
the piston must be positioned with great accuracy, this can be overcome with the use
of laser or similar accurate piston displacement measuring devices. However, there
is still a problem due to thermal expansion of the sample at the measurement
temperature control specification of 0.1C. At very low ratios the sample acts like
the Mercury in a thermometer. The expansion and contraction over a range of only
0.1C is enough to vary the small expansion ratio and reduce repeatability.
Although not mentioned in the method, one potential way to overcome this is to
measure the vapour pressure at a range of expansion ratios and extrapolate the
curve forward to obtain the vapour pressure at any desired V:L ratio.
Fig 9 Vapor pressure
curve of a crude oil
produced by an online
expansion principle
vapour pressure
analyser based on
measurement at various
V:L ratios (at 100F) and
extrapolation to 0.02:1.
As can be seen this
sample would record an
RVPE of about 5psia at
4:1 and a TVP of 26.0
psia at 0.02:1.

The expansion ratio at which the sample has a vapour pressure equal to atmospheric
pressure is termed the Gas Oil Ratio (GOR). In this case this happens at a ratio of 0.2:1.
This indicates that if one volume of oil is spilt or vented (at 100F in this case) it is expected
to release 0.2 volumes of gas to the atmosphere. So GOR can be used to estimate potential
emissions to atmosphere in the case of a spillage.
ASTM D6377 is becoming widely accepted to determine the RVPE of Crude Oil but it does
open up the possibility of measurements of Crude Oil vapour pressure based on actual
rather than artificially imposed conditions.

Appendix 1: Comparision of ASTM Vapour Pressure test Methods (many of these


methods are also adopted as ISO and other test methods under different numbers)

ASTM
No.
D323

Method

Scope

Reid vapour pressure


(two vessels) manual

D4953

Dry Reid vapour


pressure
(two vessels) manual

D5190

Automatic Method
(piston method)

D5191

Mini Method
(originally
evacuated Chamber
but now also piston
expansion)

D5482

Mini Method
atmospheric

D6377

Piston expansion
method

Gasoline, crude oil,


aviation gasoline,
other volatile
petroleum products
Gasoline, gasolineoxygenate
Blends, aviation
gasoline,
other volatile
petroleum products
Gasoline, gasolineoxygenate
Blends, aviation
gasoline,
other volatile
petroleum products
Gasoline, gasolineoxygenate
Blends, aviation
gasoline,
other volatile
petroleum products
Gasoline, gasolineoxygenate
Blends, aviation
gasoline,
other volatile
petroleum products
Crude Oil

*D6378

Triple Piston
expansion
method

D1267

Modified Reid
(two vessels)

D6897

Piston Expansion

Gasoline, gasolineoxygenate
Blends, aviation
gasoline,
other volatile
petroleum products
LPG

LPG

Test
temp
100F
(37.8C)

V:L ratio

Measured result

4:1

RVP

100F
(37.8C)

4:1

DVP (DRVP)

100F
(37.8C)

4:1

Vapour pressure
corrected to DVPE

100F
(37.8C)

4:1

Vapour pressure
corrected to DVPE

100F
(37.8C)

4:1

Vapour pressure
corrected to DVPE

5-80C

0.02:1 to
4:1

100F

4:1

Vapour pressure
corrected to RVPE
(if measured at 4:1 and 100F)
Vapour pressure corrected to DVPE
(compensates for dissolved air)

37.8C
to
70C
37.8C
to
70C

0.5:1 or
other

Vapour pressure

0.5:1 or
other

Vapour pressure

* Method D6378 uses a triple expansion method that determines the partial pressure (i.e.
that part of the measured vapour pressure) that is due to dissolved air so that it may be
subtracted. Depending how the product is made dissolved air may or may not be a
significant contributing factor to vapour pressure.