Progress in Aerospace Sciences 60 (2013) 35–44

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Progress in Aerospace Sciences

journal homepage: www.elsevier.com/locate/paerosci

Behaviour of water in jet fuel—A literature review

S. Baena-Zambrana a,n, S.L. Repetto b, C.P. Lawson a,nn, J.K.-W. Lam c
a
Cranfield University, Cranfield, Bedfordshire MK43 0AL, UK
b
University of the West of England, Coldharbour Lane, Bristol BS16 1QY, UK
c
Airbus Operations Limited, New Filton House, Filton, Bristol BS99 7AR, UK

a r t i c l e i n f o abstract

Available online 23 January 2013 This review gives a detailed account of the different types of water contaminated fuel and the conditions
Keywords: that bring about each form of contamination. It also considers studies that have been done to date that
Aviation fuel investigate the physics behind the behaviour of water in different hydrocarbons and jet fuel at low
Low temperatures temperatures.
Water & 2012 Elsevier Ltd. All rights reserved.
Ice accretion
Ice formation
Fuel system

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2. Kerosene jet fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.1. Petroleum based kerosene jet fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.2. Gas to liquid synthetic kerosene jet fuel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.3. Biokerosene jet fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3. Forms of water contamination in jet fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1. Dissolved water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.2. Free water and water-in-fuel emulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4. Hygroscopicity of jet fuel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.1. Effect of relative humidity in the solubility of water in jet fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.2. Effect of temperature in the solubility of water in jet fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.3. Effects of different hydrocarbons in the solubility of water in jet fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.3.1. Paraffins and naphthenes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.3.2. Olefins and aromatics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.4. Water solubility in jet fuel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.5. Water cycles in aircraft fuel tanks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
5. Water nucleation in fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.1. Homogeneous nucleation of water in jet fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
5.2. Heterogeneous nucleation of water in jet fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
6. Ice accretion on metal surfaces and aircraft fuel systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
7. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

1. Introduction

n
It is commonly accepted throughout the aviation industry that
Corresponding author. Tel.: þ44 7837 737 228.
nn a mixture of water and jet fuel in any form is undesirable
Principal corresponding author.
E-mail addresses: svp.baena@gmail.com, s.baena@cranfield.ac.uk (S. Baena- and potentially hazardous if the water is not managed properly.
Zambrana). Although jet engines are capable of burning a mixture of fuel and

0376-0421/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.paerosci.2012.12.001
36 S. Baena-Zambrana et al. / Progress in Aerospace Sciences 60 (2013) 35–44

water, the water content must be kept below tolerable levels, has a high molecular weight in comparison to many other
typically set at no more than 90 (water) parts per million by fuels [8].
volume (ppm-v) for normal system operation up to 260 ppm-v for Petroleum from different oil fields, and even sometimes from
emergency system operation [1,2]. Entrained or dissolved water different wells in the same field, vary greatly in the proportions of
in the fuel system, when combined with very low temperatures, the many types of hydrocarbons and individual hydrocarbons
may result in ice formation within the aircraft fuel system. present in them [9]. Hence the properties of the same type of
There are a number of systems in place to prevent the kerosene based jet fuel are dependent on the nature of the crude
adherence of ice to the fuel system surfaces. Civil aircraft prevent oil from which they are obtained.
ice build-up on fuel filters within the engine frame using fuel-oil The composition of petroleum-based jet fuel comprises (by
or fuel-air heat exchangers. Gas turbines with these systems in volume) between 99% to 99.5% pure hydrocarbons namely paraf-
place include the Rolls Royce Trent engines, Pratt & Whitney fins, naphthenes, olefins, and aromatics. It is the latter group that
and General Electric jet engines. Airbus and Boeing commercial is thought to have a greater effect on the solubility of water in jet
aircraft protect their feed pumps using mesh strainers with fuel, as discussed in Section 4.3.2.
bypasses, that ensure uninterrupted fuel flow to the engine in Approximately 0.5% to 1% of petroleum-based jet fuel consist of
the event of ice build-up and mesh strainer blockage. If conditions non-hydrocarbon components such as naphthenic acids and com-
are extremely cold, anti-icing additives are mixed with the jet fuel pounds of sulphur, sodium, lead and bromine [8]. Raw kerosene
in small quantities to prevent the formation of ice in the fuel. must meet the limits of non-hydrocarbon components set by the
These techniques address the problem, but do not necessarily Defence Standard (DEF STAN) 91-91 (or equivalent, Table 1) [5,6]. In
address the root cause. When a Boeing 777 crash landed at most cases the kerosene has to be treated in the refinery (by
Heathrow airport in January 2008, the Air Accident Investigation hydrotreating or Merox-Processing) to meet these targets. The
Branch (AAIB) final report [3] raised concerns about the lack resulting chemical composition of jet fuel varies slightly with the
of understanding of the nature and behaviour of water in jet different treatments. Recent studies have shown that the different
fuel. Hence a number of research programmes, considered in this treatments do not have a significant effect on the amount of water
review, have been initiated to further understand the behaviour absorbed by the fuel [10].
of water at low temperatures in different hydrocarbons and
jet fuels. 2.2. Gas to liquid synthetic kerosene jet fuel
In Section 2, the reader can find a general overview of jet fuels
currently utilised in the civil aviation industry. Section 3 explains Synthetic paraffinic kerosene (SPK) jet fuel is currently being
the different forms of water contamination in jet fuel. A detailed derived from natural gas using the gas to liquid (GTL) Fischer-
study of the effects of temperature and humidity on the hygro- Tropsch (FT) process [11] followed by downstream processing
scopicity of jet fuel is included in Section 4. Section 5 is the result [12]. Coal (CTL) and biomass (BTL) are also less widely used
of an extensive literature search carried out to review the current alternatives to natural gas.
understanding of water dropout and nucleation (i.e. ice forma- The FT process creates mainly straight chain hydrocarbons
tion) in aviation fuels. Section 6 gives a brief overview of ice [13]. The lack of aromatics and cyclo-paraffins in synthetic
accretion on metal surfaces and fuel systems. kerosenes yields fuels that are below the minimum density
specification requirement set at 775 kg m  3 [14]. Aromatics are
also responsible for swelling elastomers used in aircraft fuel
2. Kerosene jet fuel systems. Hence the lack of aromatics in the fuel may cause some
of these elastomers to shrink, which may lead to fuel leaks [13].
There are many different kerosene based jet fuels used in the The disadvantages discussed cease to exist if FT SPKs are blended
aviation industry [4]. The current specifications [5–7] and designa- with an aromatic-containing synthetic jet fuel, that is currently
tions for conventional jet-engined commercial aircraft are illu- derived from severely hydro-treated coal tar kerosene. It should be
strated in Table 1. These specifications are alike in most respects, noted that today SPK fuel must be blended with petroleum derived
but differ significantly in the lower freezing point, flash point, and jet fuel in order to ensure a minimum aromatic content of 8% (by
viscosity. Such characteristics are set to endure the low tempera- volume), before it can be used in commercial aircraft.
tures encountered in different countries. Sasol also produces an aromatic-containing fully synthetic
jet fuel (FSJF) that consists of 50% FT-SPK and 50% of synthetic
2.1. Petroleum based kerosene jet fuel aromatic-containing kerosene. The resulting FSJF contains the
required minimum 8% of aromatics (by volume) in the final blend
Petroleum-based jet kerosene fuels are derived from crude oil, [5,6,15].
and consists of blends of different hydrocarbons. The kerosenes In 2008, Sasol’s FSJF was approved for commercial use in all
are colourless mixtures of non-volatile petroleum fractions with types of turbine aircraft, as Jet A and Jet A-1 fuel, by the inter-
carbon chained components ranging from C9 to C14. It is this national aviation fuel authorities depicted in Table 1.
composition that determines the properties of kerosene which The solubility of water in FSJFs is approximately 25% to 30%
lower compared with conventional Jet A and Jet A-1 fuels [14]. The
Table 1 FSJFs contain less heteroatoms, aromatics and other polar com-
Worldwide petroleum based civil jet fuel grades and specifications (Russian and pounds [14]. As discussed in detail in Section 4, such compounds
former Soviet Union countries). are believed to increase water solubility in jet fuels. Research is still
required to determine the behaviour of water in fully synthetic
Fuel grade Country/Region Specification
jet fuels.
Jet A USA ASTM D1655
Jet A-1 Worldwide ASTM D1655, DEF STAN 91-91 2.3. Biokerosene jet fuel
TS-1 Russian GOST 10227
Jet Fuel no. 3 China GB 6537
Jet A & Jet A-1 Canada CAN/CGSB-3.24
Bio-synthetic paraffinic kerosene (bio-SPK) are hydropro-
cessed esters and fatty acids (HEFA) derived from plant oils and
n
Russia and CCCP animal fats [16]. During the complex process of turning biomass
 S. Baena-Zambrana et al. / Progress in Aerospace Sciences 60 (2013) 35–44 37

into fuel, plant oils and animal fats are turned into a paraffin wax lower layer separated from the jet fuel upper layer. If jet fuel and
that is later submitted to the FT process. As a result, HEFA SPK is water are mixed, they will separate back to the two layers.
almost identical to FT SPK. An emulsion is a mixture of two or more immiscible liquids
Biokerosenes were approved in the summer of 2011 [5,6,15]. where one is dispersed as droplets, of microscopic or ultra-
As with FT SPK, aromatics are not found in biokerosenes. Hence microscopic size (in this case, 0:1 mm to 100 mm water droplets),
for the reasons discussed in Section 2.2, biomass kerosenes are in the continuous phase of the other (jet fuel).
also being blended with other types of jet fuels that are able to Emulsions of water droplets in jet fuel are formed by a)
introduce aromatics in the blend. In July 2011, specific approved dissolution of water from the fuel (fully explained in Section 4.5)
bio-SPKs have been introduced in commercial aircraft as a 50/50 and b) mechanical means such as agitation as jet fuel passes
blend with petroleum derived jet fuels [17]. through different components in the fuel system. When jet
The solubility of water in bio-SPK fuels and its many blends may fuel goes through pumps in the aircraft, free water in the fuel is
be comparable to FT SPK, and is dependent on the type of jet fuel separated into a very fine dispersion of droplets of different sizes
used in the blend. Nonetheless, the hygroscopicity of biokerosenes is that lie in the range of 50 mm down to 5 mm [9].
currently part of a major European research project investigating the The rate of settling of finely dispersed water from fuel is
characteristics and specifications of alternative fuels [18]. subject to Stoke’s Law; giving the movement of water droplets a
direct proportionality to their diameter, and an inverse propor-
tionality to the fuel’s density and viscosity [9], as seen in Eq. (1),
3. Forms of water contamination in jet fuel Fig. 1.

Water can be present in fuel in three forms: dissolved in the ðrw rf Þgd
2

fuel, suspended in fuel as water-in-fuel emulsions, or free water. v¼ ð1Þ

18mf
Dissolved water is invisible to the naked eye, and is considered
a constituent of jet fuel that vaporises during combustion [8].
Water in fuel emulsions can be removed from fuel by passing
Suspended water appears as a dull, hazy, or cloudy appearance
it through water separators and filter units. These components
that takes time to coalesce or settle down. Free water, being
contain fibres with a hydrophilic surface that combines water
denser than fuel, forms a separate layer at the bottom of fuel
droplets into larger drops (Fig. 2). Larger droplets of water are not
tanks. Water-in-fuel emulsions and free water are regarded as
fuel contaminants, and are managed through rigorous Quality
Control (QC) measures [19].
Water in aviation fuel comes from numerous different sources.
Each year, a large amount of fuel is moved globally via pipeline
networks, rail, ship, road or a combination of these methods [9].
Even if the jet fuel is dry as it leaves the refinery, it may pick up
water during its transit and storage through the transport
network [8].
Means of water contamination of jet fuel include [20]:

 Rain water entering through the seals in poorly maintained

floating-roof tanks.
 Rain water entering through hatches of fuel storage tanks.
 Water left behind after cleaning operations in tanks or trans-
port vehicles due to poor personnel procedures.
 Condensation of water from moist air to the tank walls in
vented fixed roof storage tanks.
 At low temperatures, precipitation of dissolved water from the
fuel itself, as discussed in Section 4.

3.1. Dissolved water

Water is slightly soluble in jet fuel. A fuel is said to be

saturated with water when it has dissolved all the H2O molecules
it can hold under certain conditions. For example, at 21 1C and
atmospheric pressure, a saturated kerosene based fuel contains
approximately 40 to 80 ppm-v [4].
Like many other components in fuel, dissolved water is
regarded as another fuel constituent, and is not considered a
contaminant as long as it is maintained in a dissolved state [4].
Dissolved water cannot be removed by any mechanical process
such as settling, filtering or separation and so any attempt to dry
jet fuel in these ways is futile.

3.2. Free water and water-in-fuel emulsions

Water is sparingly miscible with hydrocarbon fuel and since Fig. 1. Settling times of water droplets (and rust particles Fe2O3(H2O)) in different
water is denser than fuel, any free water within the fuel forms a types of jet fuel [4].
38 S. Baena-Zambrana et al. / Progress in Aerospace Sciences 60 (2013) 35–44

usually held back for long in the fuel, forming unstable emulsions Unfortunately, maintaining an aircraft for weeks or even hours
that are easily disrupted [21]. on tarmac is not cost-effective in today’s civil aviation industry,
Substances such as naphthenic acids, phenols (both natural where turnarounds can be as short as 30 min for smaller
contents of crude oil) and sulphonic acids (introduced during commercial aircraft. Hence the pooled, free water is routinely
refining) that are present in jet fuel have an effect on the coalesce picked up and fed to the engine in a mixture with the fuel [24].
and settling of water droplets [8]. These substances act as This is part of current commonly adopted water management
surfactants by congregating at the surface of the dispersed water and is achieved using scavenging jet pumps. Free water in
droplets, forming a protective film around them that prevents the pooling points is also drained on the ground during routine
coalescence of the droplets into coarser ones, hence delaying the maintenance.
breakdown of the emulsion [8].
Stable fuel emulsions are also formed by the development of
static charges on the water droplets [21]. Under the influence 4. Hygroscopicity of jet fuel
of charges of equal sign, the droplets are repelled by each other
hence avoiding their coalescence and causing a delay on the The hygroscopic nature of jet fuel refers to its ability to attract
breakdown of the emulsion. moisture from the air and surroundings. The reversible hygro-
Demulsifiers are based on acid or base catalysed phenol-formal- scopicity of jet fuel strongly depends on atmospheric conditions
dehyde resins, polyamines, di-epoxides and polyols [23]. These are such as the temperature and relative humidity to which the jet
currently used in the crude oil industry to encourage coalescence, fuel is subjected. Any variation in these conditions will cause
making emulsions kinetically unstable. phase transitions of the water contained in the fuel.
Demulsifiers work by providing electrostatic attraction, or steric It is important to understand the difference between solubility
interaction between water droplets in the emulsion, weakening the and hygroscopicity. The solubility of water in fuel refers to the
interfacial layer of the droplets, hence making coalescence easier [8]. degree to which water dissolves in fuel to make a solution, and is
However in the aviation industry, it is imperative to deliver the fuel dependent upon the chemical composition of the fuel. Once the
to the aircraft in as clean a state as possible, thereby reducing the hygroscopic nature of jet fuel attracts moist air to its surface, the
need for the addition of enhancing additives. water molecules in direct contact with the hydrocarbon based
Several corrective measures are used in the fuel industry to fuel go into solution.
minimise the action of surfactants or static charges [24]. Under
aircraft operating conditions, the standard procedure is to allow 4.1. Effect of relative humidity in the solubility of water in jet fuel
the fuel to stand for a period of time. Emulsions are then allowed
to settle at the bottom of the fuel tanks, accumulating as free The amount of water dissolved in fuel depends on the relative
water at desired pooling points. humidity (RH) of the air above the fuel. When the fuel is not
Depending upon the nature of water-in-fuel emulsions, it may in equilibrium with the atmosphere above its surface, and its RH
take minutes, hours or weeks to coalesce and settle down. is lower than the RH of the air in the ullage, jet fuel absorbs
moisture from the air to regain a state of equilibrium according to
the surrounding conditions [9]. This process is reversible, and the
dissolved water is taken out of solution when the RH of the air
above the fuel decreases, i.e. becomes lower than the RH of
the fuel.
To have an idea of the effect of moist air within a fuel tank,
fuel in direct contact with air with a RH of 50% contains only
half as much water as water-saturated fuel at that temperature,
however fuel tends to enter the tanks of the aircraft already
saturated due to its contamination during transport from the
refinery [25].
The amount of free water accumulated in fuel storage tanks
can be significant if the tanks are located in humid climates.
Smith [9] argues that daily temperature changes in countries with
such climates are fairly small and the water released at night, is
then re-absorbed during the day, i.e. it is ‘‘self-compensating’’.
However, more recently Oreshenkov [26] has demonstrated that
over a period of a few months, cyclic temperature changes
produce a significant amount of water accumulation in fuel tanks.

4.2. Effect of temperature in the solubility of water in jet fuel

As shown in Fig. 3, there is a connection between solubility of

water in fuel and temperature. The greater the solubility of H2O in
the fuel, the higher the temperature at which dissociation of
water particles and hydrocarbon components takes place (i.e.
reversible hygroscopicity).
Water released from fuel appears as a fine cloud of minute
droplets. Lao et al. [27] measured the relative transparency of 20 L
of water saturated Jet A-1 fuel as a function of temperature. It was
observed that at temperatures above 14 1C the water was com-
pletely dissolved and the fuel had a clear appearance. As seen in
Fig. 2. Photomicrograph of coalescing process inside fibreglass media [22]. Fig. 3, at temperatures below 14 1C, excess water precipitated out
 S. Baena-Zambrana et al. / Progress in Aerospace Sciences 60 (2013) 35–44 39

Fig. 3. Water dispersed in Jet A-1 fuel [27]. (a) t ¼0 min, (b) t ¼14 min, (c) t ¼30 min and (d) t ¼58 min.

4.3. Effects of different hydrocarbons in the solubility of water in jet

fuel

Hydrocarbons are organic compounds formed of carbon and

hydrogen atoms. As discussed in Section 2, there are three main
types of hydrocarbons in jet fuel; paraffins ð  60%Þ, naphthenes
ð  20%Þ, and aromatics ð  20%Þ.
The main difference between each class of hydrocarbons is the
way in which the carbon atoms are connected to each other (as
depicted in Fig. 5), which dictates the ratio of hydrogen to carbon
atoms within the molecule. This determines the physical and
chemical properties of the fuel, including water solubility [8].

4.3.1. Paraffins and naphthenes

Paraffins and naphthenes – also known as alkanes – are the major
components of aviation fuels [8]. They consist of singly bonded
carbon chains or rings in which each atom is fully saturated with
hydrogen (i.e. saturated hydrocarbons). Paraffins can either be linear
or branched chain molecules, and the naphthenes have at least one
saturated carbon ring. The carbon–carbon and carbon–hydrogen
bonds in these molecules do not possess strong permanent dipoles
[28]; therefore this class of molecules interact with each other via the
weakest of intermolecular forces, resulting from the temporary
movement of electrons (London dispersion forces).

4.3.2. Olefins and aromatics

Olefins and aromatics (Fig. 5) are unsaturated hydrocarbons
because they contain fewer hydrogen atoms than the correspond-
Fig. 4. Water solubility vs. temperature for aircraft fuel, at 100% RH [4]. ing alkanes, and carbon–carbon double bonds, called p bonds.
The aromatics in particular have a characteristic ring of six
carbon atoms (benzene), about which the p electron cloud is
forming a fog phenomena, hence reducing the transparency of the evenly distributed. The quantity of aromatic compounds in Jet
fuel. Measured data was in agreement with the solubility of water A/A1 is limited to a maximum of 25% by volume, because of their
in fuel depicted in Fig. 4. tendency to form coke deposits on combustor surfaces, to create
40 S. Baena-Zambrana et al. / Progress in Aerospace Sciences 60 (2013) 35–44

Fig. 5. Examples of hydrocarbons commonly found in jet fuel. (a) Paraffins, (b) nephthenes, (c) olefins and (d) aromatics.

smoke when burned, and to contribute to high-luminosity flames is offset by attractive electrostatic interactions with these hydrocar-
[5,6]. bons. It has long been recognised that extended p electron systems,
such as those encountered within alkylbenzenes, form hydrogen
4.4. Water solubility in jet fuel bonds with water [34,37,38]. A weaker form of that interaction,
between water and the p bond of an alkene, may account for the
1
The hygroscopic capacity of jet fuel is determined by the water  2 kJ mol enthalpy reduction [35].
solubility of the individual hydrocarbon components. Because The formation of attractive electrostatic interactions between
water is sparingly soluble in hydrocarbons, accurate determinations water and p-aromatic systems would account for the enhanced
are difficult to achieve, and remains an active and challenging area solubility of water in alkylbenzenes, relative to both paraffins and
of research [29]. naphthenes.
Water possesses a strong permanent dipole because of the There are a number of studies that compare the solubility of
difference in electronegativity that exists between the hydrogen water in different hydrocarbons [10,27,29–44]. Most recently,
and oxygen atoms. Therefore, relatively strong attractive interac- Lam et al. [45] showed that aromatic hydrocarbons absorb up to
tions exist between adjacent water molecules, leading to four times more dissolved water than the alkane or cycloalkane
extended hydrogen bonding networks. Experimental observations with a comparable number of carbon atoms.
of water dissolution in hydrocarbons have led to a variety of As depicted in Fig. 6, water solubility increases with the
theoretical models which all require, as a first step, the disruption proportion of aromatic hydrocarbons, but not in a linear fashion.
of these hydrogen bonding networks [29–36]. Fig. 6 also reflects the behaviour of water solubility in hydro-
The energy associated with dissolving water – enthalpy of carbons in general, suggesting that this physical property is non-
solution – in a range of unbranched alkanes has only a weak colligative i.e. not simply dependent upon the number of mole-
dependence on the number of carbon atoms present (i.e. C7 C12 ¼ cules [34,43].
34.9 71.1 kJ mol  1 at 298 K) [33]. The magnitude of the enthalpy of
solution is comparable to the hydrogen bond energy, suggesting that
the dissolution of n water molecules requires the breaking of n 4.5. Water cycles in aircraft fuel tanks
hydrogen bonds [36].
The enthalpy of solution of water in both alkylbenzenes and Fuel in the aircraft system is subject to significant changes
alkenes decreases by approximately 11 and 2 kJ mol  1, respectively. in temperature and exposure to humid air within the tanks. As
The energetic cost of disrupting the hydrogen bond network of water a result of such variations and given the reversible hygroscopicity
 S. Baena-Zambrana et al. / Progress in Aerospace Sciences 60 (2013) 35–44 41

of fuel during flight, there is a continuous process of absorption Separation of water molecules from fuel also takes place as an
and spontaneous liberation of the dissolved water [4]. emulsion. If the fuel surfactants concentration is limited, the
At high altitudes and low temperatures, water from the fuel water droplets settle on the bottom of the tanks (as free water) in
evaporates until the RH of the fuel reaches equilibrium with the quiescent conditions, or remain suspended in the fuel otherwise
RH of the air within the fuel tanks. This evaporation is followed by [3,21]. Below freezing temperatures, the small droplets turn into
the condensation of the water in the ullage on the metal walls of ice crystals within the fuel and the condensed water freezes on
the tanks as well as the cold surface of the fuel. A continuous the walls or forms small ice particles on the surface of the fuel by
process of evaporation from fuel and condensation of the surplus the process of nucleation.
water vapour in the space above the fuel is established. The
evaporation process continues until the pressure of the water
vapour above the jet fuel attains an equilibrium established by 5. Water nucleation in fuels
the humidity and temperature of the air [4,21].
Nucleation is the process by which nuclei are formed, usually
in solution. The term nucleus as used in the stem of the word
refers to the formation of a small, solid phase collection of atoms,
molecules or ions during precipitation, capable of spontaneous
growth.
The metastable state of a body or system, in this case
suspended water droplets in the fuel, refers to the condition of
the water existing at an energy level in the liquid state which is
above that of a more stable condition, i.e. ice. It would take a
small amount of energy to induce a transition to the more stable
state.
Metastable states of solutions or any liquid involve both super-
saturated and supercooled solutions. Suspended water in jet fuel can
exist in a supercooled metastable phase, when supercooled water
droplets prevail inside the crystalline domain of stability [46], i.e. at
temperatures below its freezing point.
For a new phase to appear, an interface must be formed. The
creation of ice crystals from supercooled water droplets may occur
via (a) germs, or crystallites of water molecules (homogeneous
Fig. 6. Water solubility in n-Octane/Toluene mixtures at 15.5 1C. nucleation, Section 5.1) [47] or (b) germs formed upon foreign

Fig. 7. Pure water droplets in Jet A-1 fuel, cooled at 10 1C min  1 [50]. (a) T¼ 3.6 1C, (b) T¼  30.9 1C, (c) T¼  36.6 1C and (d) T¼  39 1C.
42 S. Baena-Zambrana et al. / Progress in Aerospace Sciences 60 (2013) 35–44

particles such as dust, rust or dirt (heterogeneous nucleation,  One to four centimetre long broken crystals or cotton-like
Section 5.2). fluffy mass; when there are impurities in the fuel.

5.1. Homogeneous nucleation of water in jet fuel The introduction of foreign particles and external factors
obscures and complicates the understanding of water nucleation
Classic Nucleation Theory (CNT) states that in the initial phase of in jet fuel. It adds many different parameters that are currently
homogeneous nucleation, embryos are formed as a result of sponta- the subject of wide interest in many scientific studies as well as
neous density or composition fluctuations [48,49]. The critical- sized industry projects.
embryo is in unstable equilibrium and energy is required to form a Aviation fuel in aircraft tanks may contain traces of foreign
particular cluster of molecules; embryos smaller than the critical size particulate matter such as dust or rust particles, microbiological
shrink spontaneously, releasing energy back into solution [48], while mats or sludges, crystals of benzene or paraffin, filter fibres and
embryos larger than the critical size grow spontaneously. other impurities [20] that may provide crystallisation nuclei
For a clean, uncontaminated water droplet to turn into ice, it for the nucleation of supercooled water droplets dispersed in
must first overcome an energy barrier to form a critical nucleus. the fuel. Rough surfaces and surface defects in the system may
Hobbs [48] describes different studies on homogeneous water also provide nucleation sites for crystallisation to occur. The
nucleation, establishing that for a droplet of radius of a few mm, existence of nucleation sites in supercooled water tends to speed
homogeneous nucleation becomes significant in the range of up the nucleation process, producing ice in jet fuel at tempera-
10 1C down to  40 1C. tures higher than those discussed in Section 5.1.
Murray et al. [50] investigate water drops deposited on a glass Real aircraft fuel feeding system components also add factors
slide surrounded by a matrix of Jet A-1 fuel. Water droplets of such as turbulent flow and agitation. The AAIB [3] final report
above 10 mm in diameter within the fuel are submitted to sub- reveals the formation of different forms of ice in the fuel similar to
freezing temperatures. As the temperature is lowered at a rate of that described by Ragozin [21].
10 1C min  1, most of the droplets freeze between  36 1C and
39 1C (illustrated in Fig. 7), which is in good agreement with the
results reported by Hobbs [48]. 6. Ice accretion on metal surfaces and aircraft fuel systems
In a series of similar experiments, Carpenter et al. [10]
investigate three different batches of Jet A-1 fuels as they are According to Hayashi et al. [52] the formation of frost can be
cooled down to  70 1C. At temperatures above 44 1C, there is divided in three stages, (a) crystal growth period, (b) frost layer
no evidence of the water droplets (of diameter r5 mm) changing growth period and (c) frost layer full growth period. As the frost
to crystalline ice formations. However, below  44 1C, some of the layer develops, it goes through these transformations. The frost
water droplets change to a different colour under the illumination thickness and surface temperature is gradually increased until the
of the microscope. This is explained as an indication of water melting temperature of ice water is reached. Lüer and Beer [53]
freezing as spherical droplets. Results were in good agreement demonstrated in a series of experiments that the density and
with the results reported by Murray et al. [50]. thickness of the frost surface layer depends on factors such as
time, air temperature, air velocity, air humidity and surface
5.2. Heterogeneous nucleation of water in jet fuel temperature.
Lao et al. [27] observed deposition of water/ice on the surface
The germs of H2O molecules have been regarded so far as of a sub-cooled aluminium block immersed in Jet A-1 fuel. The
isolated clusters dispersed in the liquid water, but in most cases experiments were carried out in the cold tank depicted in Fig. 3.
such germs can be encouraged to turn into ice by seeding it with a The observed deposition formed a uniform thin layer of spherical
grain of ice, or with a small particle of dust, rust or dirt [51]. This droplets on the sub-cooled aluminium surface. The characteristics
is the heterogeneous nucleation case, compared to the previously of the growth of this layer are analogous to that of the initial frost
considered homogeneous case. Homogeneous nucleation requires formation period described by Hayashi et al. [52]. However, there
a greater degree of metastability, i.e. supercooling or supersatura- was no evidence of frost layer growth on the sub-cooled alumi-
tion, than heterogeneous nucleation. nium surface. This may be due to the small and limited dissolved
Shaw et al. [51] examine the phenomenon of contact nuclea- water contained in the test rig closed fuel system, compared with
tion in a series of laboratory experiments, where a drop of pure an open system (as in the atmosphere).
water is surrounded by naphthenic oil and later by air. The study As reported by Lao et al. [27], ice accretion on a sub-cooled
compares the efficiency of an ice nucleus in causing crystallisation surface is elucidated by the Bergeron process. This theory is
when it is either immersed in the water droplet or when it is in confirmed with the observations made by Carpenter et al. [10].
contact with the droplet’s surface. The result is an estimate of the Furthermore, observations during fuel system icing tests, have
most likely temperature at which droplets freeze. demonstrated that accreted ice on sub-cooled surfaces have very
The investigation concludes that, regardless of whether the little adhesion strength. It takes minor fluid disturbances near the
water drop is surrounded by oil or air, the freezing temperature accreted ice to dislodge it from the surface. It is reasonable to
when the ice nucleus is in contact with the droplet is about postulate that ice suspended in fuel in the aircraft fuel system
4 1C–5 1C higher than when it is immersed in the droplet; there- may be the result of dislodged ice previously accreted on the
fore contact nucleation is a more effective mechanism than system sub-cooled surfaces.
immersion nucleation. The findings from the AAIB [3] are in agreement with Lao et al.
In its series of monographs Ragozin [21] describes the different [27], where ice is deposited on sub-cooled surfaces through
forms of ice encountered in jet fuel samples during a set of the Bergeron process. This occurs at higher temperatures than
experiments: the homogeneous nucleation of water droplets, indicating that
the nucleation and crystallisation of water in the fuel may be
 Minute, four-sided ice crystals; very common in undisturbed heterogeneous.
fuel. The AAIB investigations [3] suggested that at fuel temperatures
 Fluffy clumps of snow, of a dirty yellow colour or snowy mass of between  5 1C and 20 1C ice crystals tend to form in the fuel
random form; after pumping or in supersaturated conditions. and adhere to fuel system components. Under certain conditions, a
 S. Baena-Zambrana et al. / Progress in Aerospace Sciences 60 (2013) 35–44 43

Table 2 The type of nucleation of water as it slowly comes out of jet

Observations of water and ice behaviour in jet fuel at low temperatures [1,2]. fuel is an area of active interest in the research community.
During experiments, droplets can be seen in jet fuel at 14 1C,
Temperature range Water and ice behaviour observations
although other sources bring this temperature down to 10 1C. The
10 1C Z T Z 4 1C Concentration of dissolved water begins to decrease water droplets nucleate homogeneously at temperatures lower
1 1C Z T Z 3 1C Ice crystals begin to form than 35 1C.
12 1C Z T Z 18 1C Ice crystals begin to adhere to their surroundings If the fuel is agitated, there seems to be a shift in the
in the form of ice
T r 18 1C Crystals of large dimensions are formed
temperature of nucleation to temperatures just below the freez-
ing point of water (0 1C). Ice crystals and even snowflakes can be
seen in the fuel at this stage, and it is believed to be a case of
heterogeneous nucleation.
considerable amount of ice was found on the inner surfaces of the A form of ice clusters that are prone to adhere to surfaces and
cold fuel test rig. A summary of significant temperatures found in to each other has been labelled by the AAIB [3,54] as ‘‘sticky ice’’,
their investigation is exhibited in Table 2. As seen on the fourth row, and it is described as soft and porous snow. Sticky ice in fuel is
a ‘‘sticky region’’ of ice in fuel was observed between temperatures observed between temperatures ranging from 12 1C to  18 1C.
ranging from  12 1C to 18 1C. The ice adhered to fuel lines, The ice tends to adhere to fuel lines, strainers, and tank walls.
strainers, and tank walls. Hygroscopic or ‘‘shed-out’’ water is not a threat to aircraft fuel
The AAIB also observed that fuel velocity, fuel temperature and systems. These systems have robustly designed scavenge systems
water concentration in the fuel, play an important part in the that avoid the accumulation of water in remote corners in the
thickness fluctuations of ice layers within the fuel feed lines [3]. aircraft tanks. There are also a number of bypasses and fuel heaters
These factors are comparable to those that have an effect on the to prevent ice from interrupting fuel flow to the aircraft engines.
thickness and density of a frost layer [53]. Stringent QC measures are in place to deliver dry fuel to the aircraft,
as well as good maintenance procedures at airports to sump any
free water from aircraft tanks. However, the behaviour of water in
jet fuel, particularly at low temperatures, is an interesting phenom-
7. Summary enon that needs further understanding to reinforce design and
certification requirements for future commercial aircraft.
Water in jet fuel has been a topic of interest since the 1950s
when turbine-powered aircraft, flying at higher altitudes, started
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