Lube Products: Molecular D3239), and the saturated subclasses of paraffins and

cycloparaffins are measured by a different mass spectrom-

Characterization of Base Oils etry method (ASTM D2786).
Recently, the lube base oils have been characterized at the
molecular level by means of nuclear magnetic resonance
Abdul G. Abdul Jameel and S. Mani Sarathy (NMR) spectroscopy. The conventional NMR spectra have
King Abdullah University of Science and the problem of signal overlap caused by the presence of
Technology, Thuwal, Saudi Arabia CH, CH2 , and CH3 groups due to the great number of
isomers in the base oil composition.
To overcome the problem of signal overlap, some
1 Introduction 1 selected multiplet subspectral carbon-13 nuclear magnetic
resonance (13 C NMR) analyses were developed, and,
2 Base Oil Manufacture 2
in particular, gated spin echo (GASPE) and distortion-
2.1 Mineral Oils 2 less enhancement by polarization transfer (DEPT) have
2.2 Hydrocracked Base Oils 3 been applied to obtain quantitative CHn subspectra in
2.3 Hydroisomerized Base Oils 3 petroleum fractions.
2.4 Synthetic Oils 3 Usually the quantitative data obtained from GASPE,
2.5 Classification of Base Oils 4 which is a spectral editing technique, has a better accuracy
3 Base Oil Properties 4 than those from DEPT, and it will be shown how GASPE
4 Chemical Composition 5 is applied to study the molecular characteristics of the
aliphatic moieties of base oils of a different nature.
5 Conventional Base Oil Testing and Analysis 6
On the basis of the GASPE data and of the average
6 Molecular Characterization of Base Oils by molecular mass obtained via vapor pressure osmom-
Nuclear Magnetic Resonance 6 etry (VPO), the average number of branches (NB) and
7 Other Analytical Techniques 9 aliphatic rings can be calculated. Moreover, on the basis
7.1 High-performance Liquid of GASPE, the distribution of side chain lengths and the
Chromatography 10 positions of the methyl groups along the straight chain
7.2 Two-dimensional Gas Chromatography 11 (methyls are the only groups for which the positions are
7.3 Fourier Transform – Ion Cyclotron Resonance directly obtained from NMR spectra) were obtained.
Mass Spectrometry 11 These data are essential in visualizing average molecular
Acknowledgments 13 structures of different base oil components.
Besides the rich molecular diversity seen in base oils,
Abbreviations and Acronyms 13
they also possess high molecular weights (ranging from
Related Articles 13 300 to 600 Da) along with the presence of sulfur, oxygen,
References 13 nitrogen, and other heteroatoms. Data from advanced
analytical techniques along with the NMR data can be used
to get more detailed information about the composition.
Techniques such as high-performance liquid chromatog-
Base oils used in the formulation of lubricant products are raphy (HPLC), two-dimensional gas chromatography
a complex mixture of paraffins, isoparaffins, aromatic, and (GCxGC), and Fourier transform-ion cyclotron reso-
naphthenic (cycloparaffinic) molecules ranging in carbon nance (FT-ICR) mass spectrometry have been used to
number from 20 to 40+. Most automotive crankcase oils, analyze base oil composition and are discussed in the
accessory fluids, and many industrial lubricants contain in present work.
excess of 80% base oil in their ‘finished’ formulation. All these structural features are related to the finished
The molecular composition of base oils has a major lubricant’s performance in both crankcase and industrial
effect on lubricant properties, and its compositional anal- applications.
ysis is usually obtained by a two-step procedure. The
first step separates the aromatic and saturated fractions
by column chromatography (American Society for Testing
and Materials, ASTM D2549). The aromatic fraction is 1 INTRODUCTION
then further characterized by mass spectrometry (ASTM
Lubricants can be substances in all stages of matter
Update based on the original article by Luciano Montanari, Encyclopedia provided that they reduce friction and wear between
of Analytical Chemistry, © 2000, John Wiley & Sons, Ltd. materials in contact. For example, solid graphite and

Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
2 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS
molybdenum disulfide are common dry lubricants used in
high temperature applications.
The majority of lubricants are liquids. They can be
classified according to their origin into four main groups:
mineral oils derived from petroleum crude oil (the
majority); synthetic oils artificially made from chemical
compounds; vegetable oils derived from soy, castor, rape-
seed, etc.; and animal lubricants derived from animal fats.
Lubricants are also classified by the mode of application
and by the type of additives used. Most liquid lubricants
contain additives to improve their natural properties,
or give new properties to them, so they have qualities
suitable for their applications and their efficiency may be
prolonged.
Mineral lubricating oils comprising about 95% of
the lubricant market are obtained from crude oils: the
chemical composition of the crude petroleum has a great
influence on obtaining lubricating oils of the required
properties. In terms of chemical composition, crude
oils are classified into alkanic (or paraffinic) crude oils
with more than 50% alkanes, cycloalkanic or cyclic or
naphthenic crude oils with more than 50% cycloalkanes,
and aromatic crude oils with more than 50% aromatics.
Alkanic crude oils are mostly light, wax bearing, and
of low sulfur content. Cycloalkanic crude oils are often
heavy, wax-free, or of low wax content and may contain
sulfur compounds. In greater detail, the hydrocarbon
groups present in the crude oils are straight-chain and
branched alkanes, alkylcycloalkanes, alkylaromatics, and
alkylcycloaromatics.
From a property point of view, comparison of different
hydrocarbon classes of the same carbon number shows
that straight-chain alkanes (n-alkanes, n-paraffins) have
the lowest viscosity, the highest viscosity index (VI > 200),
the lowest evaporation loss, and the highest flash point.
Their pour point is high (40 ∘ C or more), and in high
concentrations they are undesirable. Generally, they are
removed from lubricating oils by solvent dewaxing or
catalytic cleavage.
Branched alkanes (isoalkanes, isoparaffins) differ from
the n-alkanes by having alkyl substituents on the main
chain. If the alkyl side chains are short and not very
numerous, the isoalkanes are similar to the n-paraffins.
On the contrary, if the alkyls are long and numerous,
isoalkanes have a low pour point, a relatively high VI, low
volatility and evaporation loss, and a high flash point. Such
isoalkanes are usually present in small amounts in the
conventional mineral oils, but they are predominant in the
unconventional oils as those obtained by hydrocracking
and hydroisomerization processes (see Section 2.3) or
manufactured synthetically (polyolefins).
Alkylcycloalkanes (naphthenes) of the same carbon
number have higher viscosity, lower VI, lower flash point,
Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
and higher evaporation loss than the alkanes and the
isoalkanes, but their pour points are generally lower.
Alkylaromatics are characterized by one or more
aromatic rings: aromatic rings have a greater effect than
the cycloalkanic ring on the viscosity of lubricating oil
cuts and at the same time decrease the VI.
2 BASE OIL MANUFACTURE
2.1 Mineral Oils
The manufacture of lubricating oils from crude oils
includes separation, refining, and dewaxing processes.
The first step is the separation process, which is the distil-
lation of the crude oil to produce gasoline, kerosene, gas
oil, and an atmospheric residue. The viscous oil cuts are
obtained from the atmospheric residue by vacuum distil-
lation. Usually the temperature does not exceed 410 ∘ C.
Vacuum distillation is normally used to produce three or
four lubricating oil distillates and vacuum asphalt. Lubri-
cating oil distillates differ from one another by distillation
range, average molecular weight, viscosity, and flash and
pour points. Base oils usually possess boiling points in the
range 288–566 ∘ C. The main criteria used are the viscosity
and the flash point.
The second step is the refining, which substantially
changes the chemical composition of lubricating oil distil-
lates and can thus control the properties of the distillates.
Its primary effect is to reduce the concentration of the
most polar constituents of the distillates. The object of
this process is to improve color, the VI, and long-term
stability. Nowadays, the most diffuse refining process is
the solvent refining, which consists of separating wax-free
oil cuts into two layers: one rich in less-polar components
and poor in solvent, called the raffinate layer or neutral
oils; the other rich in polar components and solvent, called
the extract layer. The most common selective solvents are
furfural, which is suitable for all oil stocks, and phenol,
which is used more for waxy and heavy cut oils.
The last step is the dewaxing process, which is the domi-
nant process in the recovery of oils of low pour point
and good rheological properties at low temperatures
from raffinates. The oil is diluted with the solvent, chilled
to low temperatures (10–20 ∘ C below the desired pour
point), and the separated wax crystals are filtered off.
Suitable solvents include propane, ethane, and the so-
called solvent/antisolvent mixtures, such as methyl ethyl
ketone (MEK). This process results in two products: a
dewaxed oil that contains alkanes, cycloalkanes, and some
aromatics, which forms the base stock, and a byproduct,
which is mostly paraffinic. The extract layer remaining
from solvent refining contains a high aromatic content
and is used as fuel oil. The processes described are used
LUBE PRODUCTS: MOLECULAR CHARACTERIZATION OF BASE OILS
for the production of base oils, which are, nowadays,
regarded as conventional ones.
2.2 Hydrocracked Base Oils
Although modern types of mineral oils reinforced by
additives are capable of covering a broad range of lubri-
cating requirements, their properties are in some cases
significantly surpassed by the unconventional base oils,
which include hydrocracked oils, wax hydroisomerized
oils, and polyolefin oils. Hydrocracking of oils consists
of the high-pressure (200 bar) hydrogenation of oils at
elevated temperatures (420 ∘ C) using suitable catalysts. It
improves the color and thermal stability of the oils and
also enables oils to be obtained with a high VI or even an
extremely high VI (up to 150). Hydrogenation breaks the
aromatic and naphthenic rings and changes the composi-
tion of all homogeneous oil groups: the viscosity, density,
sulfur content, and aromatic content are all reduced,
whereas the VI and hydrogen content are increased. It
also results in the removal of nitrogen compounds in the
form of ammonia. Hydrocracking enables high-grade and
high-VI oils to be produced economically. Oils of this
quality cannot be obtained by solvent refining. The supe-
riority of hydrocracked oils is in their very high VI (up to
130), good response to the additives, lower volatility at the
same viscosity, and lower biological activity. Less conve-
nient characteristics are poorer stability to light, higher
corrosiveness after oxidation, and lower solvent power for
polar substances, which are originated by oxidation.
The hydrocracked oils are generally solvent dewaxed
and, because of this, their pour points are not very low.
2.3 Hydroisomerized Base Oils
More recently, catalysts containing a hydrogenation
component on a molecular sieve have been used for wax
isomerization. They have permitted the development
of a new process for lowering the pour points of high-
wax feeds – a once-through process without requiring a
solvent dewaxer – and therefore can be used to produce
ultrahigh-VI oils with a low pour point. The oils obtained
by this process are called wax hydroisomerized oils.
Hydroisomerization dewaxing gives a higher oil yield
compared to catalytic dewaxing or solvent dewaxing with
equivalent VI.(1)
2.4 Synthetic Oils
The synthetic oils are the highest performance oils. They
are termed synthetic because they are not obtained
directly from petroleum. In comparison to mineral oil
products, synthetic lubricants have a viscosity that does
not change significantly with temperature, and their rate
of oxidation (aging) is much slower. However, the main
Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
3
disadvantage is the higher cost. They can be classified
into the following categories:
• Synthetic hydrocarbons
• Polyalphaolefins (PAO)
• Polyglycols (PAG)
• Polyether oils
• Acid esters
• Phosphoric acid esters
• Silicon-containing oils
• Halogenated hydrocarbons and halocarbons.
Synthetic hydrocarbons are produced by polymer-
ization of olefins in the presence of Lewis acids (e.g.
Al2 Cl6 , BF3 , and their complexes) or Ziegler catalyst
(e.g. Al(C2 H5 )3−x Clx and promoters) in the liquid phase.
They offer a number of advantages: they have narrow
boiling ranges and contain small quantities of unsat-
urated or polycyclic aromatic compounds and traces
of nitrogen-, sulfur-, or oxygen-containing impurities.
They have favorable low-temperature characteristics
and respond well to additive treatment. Their variable
temperature characteristics are good.
In recent years, PAO have received considerable atten-
tion as high-performance functional fluids in a variety
of applications and are the most popular synthetic lubri-
cants. They are manufactured in the presence of Lewis
acids by oligomerization of 1-alkenes in the range C8 –C12 ,
followed by hydrogenation of the double bond: they are
almost pure isoalkanes. These PAO are characterized by
high thermal stability, low viscosities even at low temper-
ature, low pour points (down to −80 ∘ C), high VI (up
to 195), high flash point, and low volatility. Almost all
of the poly(α-olefins) available today are produced from
1-decene. They can be classified into different grades
depending on their 100 ∘ C viscosities.
PAG are water-soluble lubricants (or completely oil
soluble) produced by the oxidation of alkenes followed
by polymerization reactions. They have very high VI
(up to 280), low pour point (−45 ∘ C), and better thermal
conductivity than mineral oils. Some of their other advan-
tages include low friction coefficient, low propensity for
residue formation, and hydrolytic stability.(2) Acid esters
are oxygen containing compounds produced by reacting
an alcohol with an organic acid such as adipic or azelaic
acid. Acid esters possess good low temperature prop-
erties and avoid deposit formation rendering clean hot
metal surfaces. Phosphoric acid esters are produced by
the reaction of phosphoroxytrichloride and phenol in the
presence of a catalyst. Triaryl phosphate esters are the
commonly used lubricants in the family of phosphate
esters and are employed in applications where fire safety
is an important concern. Silicone oils are inorganic
polymers containing Si O moieties connected with two
4 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS
organic groups. Polydimethylsiloxane (PDMS) is the
most commonly used silicone, which is viscoelastic and is
used as a component in silicone grease.
2.5 Classification of Base Oils
The performance of lubricating oils can be adversely
affected when base oils are switched by blenders. To
ensure that this does not negatively impact engine
performance, the American Petroleum Institute (API)
has classified base oils into five groups. Group I base
oils contain less than 90% saturates, more than 0.03%
sulfur, and VI of 80–120. These are the cheapest base
oils available in the market and are manufactured by
solvent refining. Group II base oils are produced by
hydrocracking, contain more than 90% saturates because
of which they have better antioxidation properties, and
cost more. They contain less than 0.03% sulfur and have
a VI of 80–120. Group III base oils contain more than
90% saturates and are produced by severe hydrocracking
at more intense conditions of temperature and pressure.
They can be considered as refined group II oils and
represent the best grade of petroleum-derived base oils.
They have a VI of greater than 120 and possess less than
0.03% sulfur content. Group IV base oils are synthetic
oils made of PAO and can withstand extreme conditions
of temperature. They are used in places with very hot
(Middle East) or very cold (Europe) weather. Group V
base oils are those that are not part of any of the other
four groups. These include PAG, silicone, and ester oils.
Group V oils are sometimes added with other base oils
to improve their properties. Figure 1 shows the API
classification of the base oils by Kuti et al.(3)
3 BASE OIL PROPERTIES
Lubricants are formulated by blending base oils and addi-
tives to meet a series of performance specifications. These
specifications relate to the physical properties of the oil
when it is new and also ensure that the oil continues to
function and protect the engine or machinery in service.
Self-evidently, lubricant performance is determined by
the base oils and the additives that are used in the
formulation.
When selecting the appropriate base oil to use in a
formulation, there are a range of properties that can be
measured and used to predict performance. Although
many of these properties are modified or enhanced by
the use of additives, knowledge of the base oil charac-
teristics is vital for effective formulation of any lubri-
cant. The complexity of chemical composition of the
base oils requires that most measurements are of bulk
Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
physical or chemical properties that indicate the average
performance of all the molecular types in the base oil.
The main physical properties are as follows:
• Viscosity: This is a measurement of the internal friction
within a liquid. It is a vital property of a lubricant
because it influences the ability of the oil to form a
lubricating film or to minimize friction and reduce
wear. The unit of absolute viscosity is the Pascal
second (Pa’s), although the centipoise (cP) is often
used as an alternative unit (1 Pa’s = 103 cP).
• Viscosity/temperature relationship – VI: Viscosity of
liquids decrease with increase in temperature. In high-
temperature applications, if the lubricant becomes
too thin (less viscous), then the engine components
will come in contact and increase friction. And at
low temperatures, if it becomes too viscous, then the
energy required for moving components will increase.
The most frequently used method to compare the
variation of viscosity with temperature between
different oils is by calculation of a dimensionless
number, known as the VI. The higher the VI, the less
is the effect of temperature on the viscosity of the
sample.
• Low-temperature properties: When a sample of oil is
cooled, its viscosity increases in a predictable manner
until wax crystals start to form. The matrix of wax crys-
tals becomes sufficiently dense with further cooling to
cause an apparent solidification of the oil, but it has
not undergone a true phase change. Many lubricating
oils have to be capable of flow at low temperatures and
a number of properties should be measured. Cloud
point is the temperature at which the first signs of wax
formation can be detected. Pour point is the lowest
temperature at which the sample of oil can be made
to flow by gravity alone.
• High-temperature properties: The high-temperature
properties of oil are governed by the distillation or
boiling range characteristics of the oil. Volatility is
important because it is an indication of the tendency
of the oil to be lost in service by vaporization. Several
methods are used to characterize volatility, but the
most used is the Noack method, where the sample
is heated for 1 h at 250 ∘ C, and the weight loss is
measured. The flash point of an oil is important
from a safety point of view because it is the lowest
temperature at which autoignition of the vapor occurs.
Various other physical properties may be measured,
most of them relating to specialized lubricant
applications.
The most important chemical property of base oils
is their resistance to thermal–oxidative degradation.
Although the formulated lubricant may have many
LUBE PRODUCTS: MOLECULAR CHARACTERIZATION OF BASE OILS 5

Su
lph
ur
>0
h .0 3%
hig
v ery Sa
tur
V I= ate
0 I Gr s<
r= pV ou
pI
90
rou
hu C %
Synthetics
Sulp G O, IOs) refi rude VI Minerals
PA ne oil 80
Lower pour to ns (P als in sol d i s –1
r
ila lefi ic to ve phy dist 20
Lower
point Sim rnalo chem cess als nts, sicall illed,
t e n t r o fin o b and y w sulphur
lyln re is p n a b ished e hyd may ith

Sulphur <0.03% Saturates >90% VI 80–120

Po diffe thes n eve as , to ro
u e e syn ive a er VI
s by- e sto leav -
th g igh pro ck e
h du and
All base stocks not classified
Sulphur = 0 VI = very high

cts
in other groups, including

Crude oil is distilled and

vegetable oil derived

hydrogenation, to leave
base stocks, esters,

chemically refined by
a base stock with
Group V

by-products
diesters,
glycols,

Group II
etc.

fewer
po (PA il is
l e o and re
are yalph O) u d
Cr tilled seve
s a
sto ynth chem olfin dis d by and ,
cks esi ica s ne ing ion VI
s
VI with ed b lly r fi rack enat gher ewer
e
Gr com incr ase c rog i
a h en
f
ou pa
p I red ease hyd uce d ev s
Higher flash II s d d n t
toc to pro k a uc
point ks to stoc -prod
Gr s e b y 0
Su ou ba II I >12
VI Higher VI
lph pI
V oup
ur
=0 Gr > 90%
VI ates
=v tur
ery Sa
hig
h 0. 03%
hu r<
S ulp

Purer

Figure 1 API classification of base oils. (Reproduced with permission from Ref. 3. © Elsevier, 2015.)

desirable properties when new, oxidation can lead to a for improved fuel efficiency, which is being driven by
dramatic loss of performance in service by oxidative reac- both legislation and product specification. This requires
tions. Oxidation of lubricants is influenced by a variety of a deep knowledge of the molecular characteristics of
factors such as engine temperature, O2 exposure, water the base oils, which is not easy because they consist
contamination, presence of metallic debris, efficiency of of large numbers of structurally different compounds.
additives, and the type of base oil used.(4) A variety of A large number of correlations based on the relative
different stability tests have been devised to measure distribution of paraffinic-, aromatic-, and naphthenic-type
resistance to oxidation such as total acid number (TAN) hydrocarbons are reported in the literature,(5,6) but these
and breakdown number (BDN) under different condi- studies do not involve the nature and distribution of the
tions. aliphatic moieties, which, vice versa, determine the low-
temperature and rheological properties of base stocks.
Proton nuclear magnetic resonance (1 H NMR) and 13 C
4 CHEMICAL COMPOSITION NMR techniques have also been used to estimate struc-
tural parameters in petroleum cuts,(7–11) but they have
Even if the properties of lubricating oils are largely due limitations in resolving the resonance of CHn (n = 0–3)
to the additives, the importance of the chemical compo- groups in the aliphatic region mostly due to overlapping
sition of base oils on the finished lubricant performance paraffinic and naphthenic CH2 signals. 1 H NMR and 13 C
is increasing more and more and this is particularly true NMR have also been the techniques of choice to study

Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
6 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS
the molecular structure of other petroleum-derived fuels
such as gasoline, diesel, and heavy fuel oils.(9–13)
To overcome the problem of signal overlap, some
selected multiplet subspectral 13 C NMR analyses were
developed and, in particular, GASPE has been applied
to obtain quantitative abundances of CHn groups in
petroleum fractions.(14,15) GASPE/NMR(16) was used to
compare different base oils: mineral, hydrocracked, wax
hydroisomerized, PAO, and poly(internal olefins). From
GASPE spectra the fractional abundances of CHn , the
number and length of branches, the position of methyl
groups along the straight chain, and the average number
of aliphatic rings (NAR) were obtained.
5 CONVENTIONAL BASE OIL TESTING
AND ANALYSIS
The testing of lubricants is based on chemical and phys-
ical properties and on parameters that represent statis-
tical means of the molecular properties. The essential
methods have been standardized on an international basis
by organizations such as the ASTM (USA), the Insti-
tute of Petroleum (IP, UK), the Deutsches Institut fur
Normung (DIN, Germany), and the International Orga-
nization for Standardization (ISO). Hereafter, the most
diffuse tests for analysis of physical properties and hydro-
carbon type are summarized:
• Viscosity: Kinematic viscosity is measured routinely
with ease and great precision in capillary viscome-
ters suspended in constant-temperature baths. Stan-
dard methods are ASTM D445 and IP 71, and a
number of standard temperatures are used, especially
40 and 100 ∘ C. It can also be measured using a Zhan
cup, vibrational viscometer, rotational viscometer, and
falling sphere viscometer.
• Viscosity/temperature relationship – VI: VI are calcu-
lated by measuring the kinematic viscosities of the
sample at two different temperatures (40 ∘ C, 100 ∘ C)
and comparing the viscosity change with an empir-
ical reference scale. Full definitions of the methods of
calculation are given in ASTM or IP manuals (ASTM
D2270, IP 226).
• Low-temperature properties: The pour points are
measured with the manual ASTM D97 and IP 15, in
which the oil is warmed and then cooled at a specified
rate until the lowest temperature is reached at which
the sample can be made to flow by gravity alone. In
the automatic ASTM D5949 method, the oil is heated
and cooled by a Peltier device. The sample is moni-
tored continuously using multiple optical detectors to
detect movement at the sample surface.
Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
• Volatility: This is important because it is an indica-
tion of the tendency of oil to be lost in service by
evaporation. Generally, it is measured with the Noack
method, where the sample is heated for 1 h at 250 ∘ C,
and the weight loss is measured (ASTM D5800 and
DIN 51581).
• Hydrocarbon analysis: The detailed hydrocarbon
analysis is obtained by a two-step procedure. The first
step separates the aromatic and saturated fractions
by column chromatography (ASTM D2549). The
aromatic fraction is then characterized further by
mass spectrometry (ASTM D3239), and the satu-
rated subclasses of paraffins and cycloparaffins are
measured by a mass spectrometry method (ASTM
D2786).
6 MOLECULAR CHARACTERIZATION OF
BASE OILS BY NUCLEAR MAGNETIC
RESONANCE
NMR is the most important spectroscopic technique
available for molecular characterization of the hydro-
carbon skeleton. On the basis of the positions and
intensities of signals, it is possible to identify the types
and number of different nuclei, especially H and C
in organic compounds. Some important books(17,18)
describe the fundamentals of this spectroscopy, which is
widely used in different fields such as chemistry, physics,
medicine, and pharmaceutics.
1 H and 13 C NMR techniques have been utilized for
the estimation of structural parameters of low- and high-
boiling petroleum cuts such as gasoline, kerosene, and
diesel. The 1 H NMR spectra of base oils consist of two
main types of signal (Figure 2): a broad resonance at
6.5–8 ppm due to H atoms bonded to aromatic carbons
and signals at 2–0.5 ppm due to H atoms bonded to
aliphatic carbons. In the aliphatic regions it is possible to
observe the signal corresponding to H atoms of methyl
(CH3 ) groups in paraffinic chains at nearly 0.8 ppm and a
sharp signal at nearly 1.25 ppm due to H atoms of methy-
lene (CH2 ) groups in paraffinic chains.
The 13 C NMR spectra of base oils (Figure 3) show
the signals due to aromatic carbons between 100 and
150 ppm and those of the aliphatic carbons in the region
0–50 ppm.
Particularly in the aliphatic regions there are a
great number of peaks due to branched paraffins and
cycloparaffins: some structural assignments have been
proposed,(19) but they refer predominantly to the promi-
nent peaks, whereas a great part of the signal is due
to the multiplicity of weak resonances spread over the
spectral width. The chemical shift region between 1.4 and
2.05 ppm contains overlapping signals of H atoms of CH
LUBE PRODUCTS: MOLECULAR CHARACTERIZATION OF BASE OILS 7

CDCl3 solvent

9 8 7 6 5 4 3 2 1 0 160 140 120 100 80 60 40 20 0

(ppm) (ppm)

1
Figure 2 H NMR spectrum of base oil A (Table 1). Figure 3 13
C NMR spectrum of base oil A (Table 1).

and CH2 groups present in cycloalkanes and isoalkanes.
The region between 2.05 and 2.8 ppm corresponds to
overlapping signals of H atoms (in CH, CH2 , and CH3
groups) in alpha position to an aromatic ring.(20) The
isomeric forms present originate from these later; for
instance, there are over 360 000 noncyclic alkane isomers
for C20 alkanes, and this number rapidly increases for
heavier alkanes. In conventional 13 C NMR spectra, it is
very difficult to resolve the resonances of CHn (n = 0–3)
in the aliphatic region.
To overcome this problem, GASPE a multiphase,
spectral editing technique based on proton multiplicity
has been quite useful because it allows the generation of
quantitative CHn subspectra.
An example of the application of the GASPE
technique is shown in Figure 4: the 13 C NMR
spectrum of the squalane molecule (2,6,10,15,19,23-
hexamethyltetracosane) (Figure 4), which is used as
a model compound for base oil, is divided into three
subspectra with the C assignments reported in the figure.

CH3 CH3 CH3

H3C
CH3
CH3 CH3 CH3

CH3

CH2

CH

All CHn

50 40 30 20 10
(ppm)

Figure 4 Conventional 13 C NMR (bottom) spectrum of squalane (whose molecular structure is on the top). The GASPE subspectra
are labeled according to the component resonance types as CH, CH2 , and CH3 .

Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
8 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS

Table 1 List of the 17 analyzed lubricating base oils CH + CH3

a
Base oil Class
A SR
B SR
C SR
D SR CH2
E SR
F HISO
G HISO
H HISO
I HC + HISO
L HC C
M HC
N HC
O HC
P HC
Q PAO ∑nCHn
R PIO
S PAO
50 40 30 20 10
a SR,solvent-refined mineral oils; HISO, hydroisomerized; HC, hydroc-
(ppm)
racked; PAO, poly(α-olefin); PIO, poly(internal olefin).

Figure 5 Conventional 13 C NMR (bottom) spectrum of base

oil F (aliphatic region). The GASPE subspectra are labeled
The molecule of squalane has the following CHn according to the component resonance types as C, CH2 , and
groups: (CH3 )8 (CH2 )12 (CH)6 . The respective CHn CH + CH3 .
fractions according to Equation (1):

I(CHn )
22.6

19.6

16.4
14.5
14.3
14.0

11.3
10.8
F(CHn ) = ∑ (1)
I(CHn )
n

where I(CHn ) is the total NMR signal intensity of

the CHn groups. The F(CHn ) fractions from NMR are
F(CH) = 0.20; F(CH2 ) = 0.53; F(CH3 ) = 0.27. The F(CHn )
fractions calculated from GASPE are F(CH) = 0.21;
F(CH2 ) = 0.53; F(CH3 ) = 0.26. Comparing the data
obtained by GASPE with the real values, the GASPE
technique results are very accurate.
We have analyzed a few different types of base oils
by GASPE/NMR, and in Table 1 they are summarized
using letters to define their nature. In Figure 5, the
GASPE/NMR spectra of base oil F, as a general example, 20 15 10
are shown. (ppm)
Another advantage of GASPE spectra is to have the
methyl signals without the presence of CH2 signals in the Figure 6 GASPE CH3 13
C NMR subspectra of base oil F as a
region between 5 and 30 ppm. The methyl signals can be general example.
assigned to specific branching sites along the hydrocarbon
chain. An example of the methyl region of the GASPE
spectrum is shown in Figure 6. The main signals of methyl by multiplying the molar fraction of methyls, F(CH3 ),
groups are assigned to the hydrocarbon branches shown by the average number of carbons (NC ) of the base oil,
in Table 2. obtained by VPO, which gives the average number of
On the basis of GASPE data, some molecular features methyls per molecule, and then subtracting two from the
have been calculated relating to the NB and the NAR resulting product (the two terminal methyls of the straight
for an average molecule. From GASPE spectra the chain). The expression is as shown in Equation (2):
molar fractions of the CHn (n = 0–3) aliphatic group are
obtained using Equation (1). The average NB is estimated NB = nCH3 − 2 = F(CH3 )NC − 2 (2)

Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
LUBE PRODUCTS: MOLECULAR CHARACTERIZATION OF BASE OILS 9

Table 2 Methyl peak assignment of the CH3 GASPE/13 C (GC)/mass spectrometry (ASTM D2549, ASTM D3239,
NMR subspectrum of hydrocarbon base oil and ASTM D2786). The volume percentages of isoparaf-
Type of branch δ (ppm) Identification no. fins, cycloparaffins, and aromatic compounds are reported
in Table 5, and the physical and rheological properties of
>CHCH2 CH3 10.8 1
–(CH3 )CHCH2 CH3 11.3 2 the same analyzed base oils are reported in Table 6.
>CHCH2 CH2 CH3 14.5 3 From the analysis of Tables 1–5, it is evident that the
–CH(CH3 )CH2 CH2 CH3 14.3 4 molecular features are peculiar to different classes of
–(CH2 )nCH2 CH2 CH2 CH3 14.0 5 base oils. For instance, the SR (solvent-refined) mineral
–CH2 CH(CH3 )–CH< 17–15 6 base oils have a greater content of aromatics (vol.% and
–CH2 CH(CH3 )–CH2 – 19.6 7
–CH2 –CH(CH3 )2 22.6 8 their H and C fractions), whereas the polyolefins have
a greater fraction of methyl groups on long aliphatic
chains (identification number 6 in Table 2). These chem-
ical features certainly influence the physical properties of
The NAR can be calculated according to Equation (3): the base oils: for instance, the higher value of aromatics
in SR mineral oils is the cause of their higher pour points,
[ ]
NAR = 0.5NC 2F(C) + F(CH) − F(CH3 ) + 1 (3) whereas the presence of long chains in the polyolefins
should be the cause of their excellent pour points. Several
Other molecular characteristics are obtained directly models have been proposed in the literature to predict
from the NMR spectra: for instance, the molar fractions the properties of base oil such as VI, volatility, API
of aromatic hydrogens and carbons are calculated using gravity, aniline point, and pour point using the structural
Equation (4): data derived from NMR spectroscopy and artificial neural
networks.(6,21,22) Certainly the possibility of having predic-
I(H ) I(C ) tive models of the performance of finished oils based on
F(Har ) = ∑ ar F(Car ) = ∑ ar (4)
I(Hn ) I(Cn ) the molecular characteristics of base oils could represent
n n a very valid tool for lubricant manufacturer choice, espe-
cially for the formulation of lubricants with very high
where the denominators are the sum of all spectral inten- performance.
sities of the relative nuclei. In Table 3, the molecular
features of the 17 base oils of Table 1 are shown, with the
acronyms used in the text.
In Table 4, the molar fractions of different methyl 7 OTHER ANALYTICAL TECHNIQUES
groups with the identification numbers reported in
Table 2 are shown. The hydrocarbon-type analysis of Base oils contain thousands of individual molecules with
each base oil was carried out with gas chromatography multiple chemical functionalities along with heteroatoms

Table 3 Molecular features of the analyzed base oils

Base oil F(Har ) F(Car ) F(C) F(CH) F(CH2 ) F(CH3 ) NC NB NAR
A 0.8 0.07 0.02 0.14 0.59 0.18 30 3.4 1.0
B 1.1 0.07 0.02 0.15 0.56 0.20 28 3.6 0.9
C 1.5 0.09 0.02 0.14 0.56 0.19 29 3.5 0.9
D 1.3 0.07 0.02 0.14 0.58 0.19 29 3.5 0.9
E 1.4 0.09 0.02 0.14 0.58 0.17 36 4.1 1.0
F 0.0 0.00 0.00 0.14 0.68 0.18 36 4.5 0.3
G 0.0 0.00 0.00 0.13 0.72 0.15 33 3.0 0.7
H 0.0 0.00 0.00 0.12 0.70 0.18 30 3.4 0.1
I 0.0 0.00 0.02 0.11 0.68 0.19 32 4.1 0.4
L 0.2 0.01 0.00 0.14 0.68 0.17 30 3.1 0.6
M 0.2 0.01 0.01 0.14 0.66 0.18 32 3.8 0.7
N 0.0 0.00 0.03 0.12 0.67 0.18 29 3.2 1.0
O 0.0 0.00 0.01 0.13 0.66 0.20 34 4.8 0.2
P 0.5 0.02 0.03 0.11 0.66 0.18 32 3.8 0.8
Q 0.0 0.00 0.00 0.12 0.73 0.15 33 3.0 0.5
R 0.0 0.00 0.02 0.11 0.70 0.17 35 4.0 0.7
S 0.0 0.00 0.02 0.08 0.75 0.15 44 4.6 0.3

Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
10 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS

Table 4 Molar percentages of methyl groups on different branches, numbered as in Table 2

Base oil 1 2 3 4 5 6 7 8
A 3.3 4.7 1.1 4.0 28.9 6.3 39.2 12.5
B 1.1 3.1 1.6 4.6 20.2 9.0 44.7 15.7
C 1.3 4.0 1.8 6.6 24.2 8.6 40.8 12.7
D 1.2 4.0 2.0 8.0 24.2 7.2 39.8 13.6
E 1.5 2.8 3.3 6.2 22.8 8.1 41.7 13.6
F 9.0 5.1 7.1 4.2 23.1 4.9 36.5 10.1
G 8.9 5.3 6.6 3.0 30.1 2.8 33.9 9.4
H 7.1 4.5 7.9 3.8 26.1 6.2 31.8 12.6
I 6.2 5.1 6.4 4.3 22.4 6.7 36.3 12.6
L 7.5 5.2 4.5 4.8 32.4 3.5 30.9 11.2
M 4.5 4.2 5.4 4.7 19.7 7.5 39.2 14.8
N 6.0 4.5 8.0 4.9 27.9 5.3 32.2 11.2
O 5.4 5.6 7.0 4.6 26.1 4.3 33.4 13.6
P 5.1 4.1 5.7 4.1 25.8 8.1 34.9 12.2
Q 1.7 0.8 6.6 0.0 75.7 11.9 3.3 0.0
R 3.3 3.5 2.8 1.8 62.2 8.8 17.6 0.0
S 2.6 0.0 8.1 0.0 72.5 13.3 3.5 0.0

Table 5 Volume percentage (vol.%) distribution of isoalkanes, cycloalkanes, and aromatics

Base oil Isoalkanes (vol.%) Cycloalkanes (vol.%) Aromatics (vol.%)
A 23.8 55.1 21.1
B 20.0 61.9 18.1
C 21.1 48.4 30.5
D 23.7 51.7 24.6
E 15.8 47.6 36.6
F 79.1 20.0 0.9
G 80.5 19.2 0.3
H 86.2 13.2 0.6
I 71.1 28.3 0.6
L 65.6 30.4 4.0
M 31.3 66.1 2.6
N 75.8 23.6 0.6
O 53.0 46.4 0.6
P 55.0 39.8 5.2
Q 97.0 3.0 0.0
R 82.9 17.1 0.0
S 97.0 3.0 0.0

(O, N, S, etc.). Also these molecules are spread across a
wide range of molecular weights and therefore require
multiple analytical methods for structure elucidation. A
number of techniques have been utilized to study the
chemical composition of base oils, which include infrared
(IR) spectroscopy,(23,24) gas chromatography mass selec-
tive detector (GC-MSD),(25) and X-ray spectroscopy.(26)
Techniques such as NMR spectroscopy when comple-
mented with other analytical techniques can provide
more detailed information about the molecular structure.
Following are some useful analytical techniques that have
been used to characterize base oils.
7.1 High-performance Liquid Chromatography
HPLC is a column chromatography technique where
the sample is dissolved in a solvent (mobile phase)
such as heptane and pumped through a solid column
(stationary phase) made of adsorbent material at high
pressures. The different molecules in the sample interact
differently with the column leading to their separation
and subsequent identification and quantification. HPLC
can provide reliable group-type compositional data of
the compounds (low to high boiling range) in base oils.
The HPLC data is semiquantitative in nature, calculated
from the relative peak area of each group. Hourani

Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
LUBE PRODUCTS: MOLECULAR CHARACTERIZATION OF BASE OILS 11

Table 6 Physical and rheological properties of base oils

Base oil Pour point (∘ C) Kinematic viscosity Kinematic viscosity VI Noack (% w/w)
at 40 ∘ C (cSt) at 100 ∘ C (cSt)
A −9 29.69 5.23 107 11.6
B −9 31.61 5.32 100 14.1
C −9 31.17 5.29 101 11.2
D −12 29.45 5.22 108 12.0
E −9 95.38 10.71 95 2.6
F −21 23.57 5.04 146 12.4
G −24 29.67 5.79 141 7.5
H −21 21.07 4.69 146 15.1
I −18 27.14 5.52 146 11.8
L −27 17.69 4.02 127 14.8
M −21 32.65 5.94 128 6.0
N −27 18.49 4.14 129 10.7
O −15 32.93 5.92 125 7.6
P −9 34.67 6.15 126 4.5
Q −60 29.67 5.90 147 4.8
R −45 30.36 5.70 131 8.2
S −63 45.55 7.68 137 4.0

et al.(27) used HPLC and analyzed five samples of group I
and III base oils into saturates and aromatics groups.
The aromatic groups were further differentiated into
mono-, di-, and triaromatics. Espada et al.(28) used HPLC
to separate lubricating oil feedstock into saturated and
aromatic fractions. Elemental analysis (carbon, hydrogen,
sulfur; CHS), 1 H and 13 C NMR experiments were then
performed to generate average molecular structures of
the base oils.
7.2 Two-dimensional Gas Chromatography
In (GC, the sample is vaporized using an inert carrier gas
(mobile phase) such as helium or N2 , which then passes
through a layer of liquid or polymer supported on an
inert solid (stationary phase). One-dimensional GC and
also high-resolution GC are unable to completely resolve
complex mixtures such as base oils. The chromatogram
shows an elevated baseline (hump) due to the unresolved
high boiling components in the sample. This limitation can
be overcome (or reduced) using GCxGC column, which
can separate components with higher molecular weights
that a single column cannot handle. The complete sepa-
ration of the saturates (paraffins and naphthenes) in base
oils may still not be accomplished owing to the molecular
complexity of base oils.(27,29) Hourani et al.(27) character-
ized five base oil samples using GCxGC and Figure 7
shows the chromatogram obtained for a group I base oil.
GCxGC provided comprehensive data on the composi-
tion of the different saturates and aromatic families (such
as mono-, di-, and triaromatics) and the carbon number
range. The five base oil samples consisted of saturates
ranging between 57.6 and 81 wt%, whereas the aromatics
ranged between 19 and 42.4 wt%. The paraffinic families
displayed carbon number in the range 17–37, whereas the
monoaromatic families ranged between 16 and 28+.
7.3 Fourier Transform – Ion Cyclotron Resonance
Mass Spectrometry
FT-ICR mass spectrometry is a technique to determine
the mass-to-charge (m/z) ratio of ions in a fixed magnetic
field based on the cyclotron frequency. In other mass
spectrometry techniques, the ions are detected by hitting
a detector, whereas in FT-ICR mass spectrometry the
ions pass near detection plates. High-resolution data can
be obtained by this technique as the superconducting
magnet employed is more stable than the RF voltage
used in other mass spectrometry techniques. It has been
extensively applied in determining the composition of
complex molecules based on their accurate mass. The
high resolution (narrow peak width) allows for two
ions with the same mass-to-charge ratio be detected
as different ions. FT-ICR mass spectrometry is used
in conjunction with various ionization techniques for
ionizing the samples. Ionization techniques such as
atmospheric pressure chemical ionization (APCI) and
atmospheric pressure photoionization (APPI) have been
widely used to ionize complex hydrocarbon mixtures
such as base oils. Figure 8 shows the FT-ICR mass spectra
of three base oils reported by Kuti et al.(3) FT-ICR mass
spectrometry can further resolve the aromatic groups
into napthenic and alkyl-substituted groups. The carbon
number breakdown of base oils(27) showed the presence
of high molecular weight components of up to 90 C
atoms, which can only be detected by FT-ICR mass
spectrometry.

Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
12 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS

000
6.000

NTrA
TrA

NDA
5.000

DA
4.000

NMA
3.000
2.000

MA
1.000

nP+iP+MN

66.667 75.000 83.333 91.667 100.000 103.333 116.667 125.000 133.333

Figure 7 Two-dimensional gas chromatogram obtained for lube oil BO-1 sample: P, normal paraffins and isoparaffins; N, naph-
thenes; MN, mononaphthenes; MA, monoaromatics; NMA, naphtheno-monoaromatics (two rings, one saturated and one aromatic);
DA, diaromatics; NDA, naphtheno-diaromatics (three rings, one saturated and two aromatic); TrA, triaromatics; NTrA, naphtheno-
triaromatics (four rings, one saturated and three aromatic). (Reprinted with permission from Ref. 27. Copyright 2015 American
Chemical Society.)

Intens. APCI_pos_sample_SN100_000002.d: +isCID MS
×108 369.351583
6 663.453688
551.503400
4
257.247505
2
815.213995
0
×108 APCI_pos_sample_HC4_000003.d: +isCID MS
411.398536 663.453611
6
577.134036
4
2
815.213755
0
×108 663.453641 APCI_pos_sample_HC6_000001.d: +isCID MS
6
411.398542 483.492455 577.134059
4

2
815.213845
0
200 300 400 500 600 700 800 900 1000 m/z

Figure 8 FT-ICR mass spectra of Group 1 (SN100) and Group III (HC4 and HC6) base oils. (Reproduced with permission from
Ref. 3. © Elsevier, 2015.)

Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
LUBE PRODUCTS: MOLECULAR CHARACTERIZATION OF BASE OILS 13

ACKNOWLEDGMENTS Environment: Water and Waste

Nuclear Magnetic Resonance for Environmental
The authors acknowledge the funding from King Monitoring
Abdullah Research of Science and Technology (KAUST)
Industrial Hygiene
and Saudi Aramco under the FUELCOM program.
Spectroscopic Techniques in Industrial Hygiene
Petroleum and Liquid Fossil Fuels Analysis
Lubricant Base Oils: Analysis and Characterization
ABBREVIATIONS AND ACRONYMS of • Nuclear Magnetic Resonance Characterization of
13 C Petroleum • Petroleum Residues, Characterization of
NMR Carbon-13 Nuclear Magnetic Resonance
1HNMR Proton Nuclear Magnetic Resonance Process Instrumental Methods
APCI Atmospheric Pressure Chemical Ionization Nuclear Magnetic Resonance and Magnetic Resonance
API American Petroleum Institute Imaging for Process Analysis
APPI Atmospheric Pressure Photoionization Nuclear Magnetic Resonance and Electron Spin Reso-
ASTM American Society for Testing and Materials nance Spectroscopy
BDN Breakdown Number Nuclear Magnetic Resonance and Electron Spin Reso-
CHS Carbon, Hydrogen, Sulfur nance Spectroscopy: Introduction • Nuclear Magnetic
DEPT Distortionless Enhancement by Polarization Resonance Instrumentation • Nuclear Magnetic Reso-
Transfer nance of Geological Materials and Glasses • Parameters,
DIN Deutsches Institut fur Normung Calculation of Nuclear Magnetic Resonance • Zeeman
FT-ICR Fourier Transform-ion Cyclotron Resonance Interaction in Nuclear Magnetic Resonance
GASPE Gated Spin Echo
GC Gas Chromatography
GCxGC Two-dimensional Gas Chromatography REFERENCES
GC-MSD Gas Chromatography Mass Selective
Detector 1. Q. Wang, H. Ling, B. Shen, K. Li, S. Ng, ‘Evaluation of
HPLC High-performance Liquid Chromatography Hydroisomerization Products as Lube Base Oils Based
IP Institute of Petroleum on Carbon Number Distribution and Hydrocarbon Type
IR Infrared Analysis’, Fuel Process. Technol., 87(12), 1063–1070
ISO International Organization for (2006).
Standardization 2. R. Van Voorst, F. Alam, ‘Polyglycols as Base Fluids for
MEK Methyl Ethyl Ketone Environmentally-Friendly Lubricants’, J. Synth. Lubr.,
NAR Number of Aliphatic Rings 16(4), 313–322 (2000).
NB Number of Branches 3. O.A. Kuti, S.Y. Yang, N. Hourani, N. Naser, W.L. Roberts,
NMR Nuclear Magnetic Resonance S.H. Chung, S.M. Sarathy, ‘A Fundamental Investigation
PAG Polyglycols into the Relationship Between Lubricant Composition and
PAO Polyalphaolefins Fuel Ignition Quality’, Fuel, 160, 605–613 (2015).
PDMS Polydimethylsiloxane 4. H. Omrani, A.E. Dudelzak, B.P. Hollebone, H.-P. Loock,
SR Solvent-refined ‘Assessment of the Oxidative Stability of Lubricant oil
TAN Total Acid Number Using Fiber-Coupled Fluorescence Excitation–Emission
VI Viscosity Index Matrix Spectroscopy’, Anal. Chim. Acta, 811, 1–12 (2014).
VPO Vapor Pressure Osmometry
5. A.J. Stipanovic, M.P. Smith, G.P. Firmstone, J.A. Patel
(1994) ‘Compositional Analysis of Re-Refined and
Non-Conventional Lubricant Base Oils: Correlations to
RELATED ARTICLES Sequence VE and IIIE Gasoline Engine Tests’, SAE
Technical Paper 941978.
6. A. Adhvaryu, J.M. Perez, L.J. Duda, ‘Quantitative NMR
Chemical Weapons Chemicals Analysis
Spectroscopy for the Prediction of Base Oil Properties’,
Nuclear Magnetic Resonance Spectroscopy in Analysis of Tribol. Trans., 43(2), 245–250 (2000).
Chemicals Related to the Chemical Weapons Convention
7. P.F. Barron, M.R. Bendall, L.G. Armstrong, A.R. Atkins,
Coatings ‘Application of the DEPT Pulse Sequence for the Gener-
Nuclear Magnetic Resonance of Coating and Adhesive ation of 13 CHn Subspectra of Coal-Derived Oils’, Fuel,
Systems 63(9), 1276–1280 (1984).

Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
14
8. V. Calemma, P. Iwanski, M. Nali, R. Scotti, L. Montanari,
‘Structural Characterization of Asphaltenes of Different
Origins’, Energy Fuel, 9(2), 225–230 (1995).
9. A.G. Abdul Jameel, A.M. Elbaz, A.-H. Emwas, W.L.
Roberts, S.M. Sarathy, ‘Calculation of Average Molecular
Parameters, Functional Groups, and a Surrogate Molecule
for Heavy Fuel Oils Using 1 H and 13 C Nuclear Magnetic
Resonance Spectroscopy’, Energy Fuel, 30(5), 3894–3905
(2016).
10. A.M. Elbaz, A. Gani, N. Hourani, A.-H. Emwas, S.M.
Sarathy, W.L. Roberts, ‘TG/DTG, FT-ICR Mass Spec-
trometry, and NMR Spectroscopy Study of Heavy Fuel
Oil’, Energy Fuel, 29(12), 7825–7835 (2015).
11. A.G. Abdul Jameel, N. Naser, A.-H. Emwas, S. Dooley,
S.M. Sarathy, ‘Predicting Fuel Ignition Quality Using 1
H NMR Spectroscopy and Multiple Linear Regression’,
Energy Fuel, 30(11), 9819–9835 (2016).
12. A.G. Abdul Jameel, S.M. Sarathy, ‘Prediction of RON and
MON of Gasoline-Ethanol Using 1 H NMR Spectroscopy’.
Proceedings of the European Combustion Meeting, 2017.
13. A.G. Abdul Jameel, Y. Han, O. Brignoli, S. Telalović,
A.M. Elbaz, H.G. Im, W.L. Roberts, S.M. Sarathy, ‘Heavy
Fuel oil Pyrolysis and Combustion: Kinetics and Evolved
Gases Investigated by TGA-FTIR’, J. Anal. Appl. Pyrol-
ysis, 127(August), 183–195 (2017).
14. D. COOKSON, B. SMITH, ‘Determination of Carbon C,
CH, CH2 and CH3 Group Abundances in Liquids Derived
from Petroleum and Coal Using Selected Multiplet 13 C
NMR Spectroscopy’, Fuel, 62(1), 34–38 (1983).
15. D.J. Cookson, C.L. Rolls, B.E. Smith, ‘Structural Charac-
teristics of Branched Plus Cyclic Saturates from Petroleum
and Coal Derived Diesel Fuels’, Fuel, 68(6), 788–792
(1989).
16. L. Montanari, E. Montani, C. Corno, S. Fattori, ‘NMR
Molecular Characterization of Lubricating Base Oils:
Correlation with their Performance’, Appl. Magn. Reson.,
14(2–3), 345–356 (1998).
17. H. Gunther, NMR Spectroscopy: Basic Principles,
Concepts and Applications in Chemistry, 3rd edition,
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 734,
2013.
18. J. Keeler, Understanding NMR Spectroscopy, John Wiley
& Sons, Inc., New Jersey, 2010.
Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1824.pub2
PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS
19. A.S. Sarpal, G.S. Kapur, A. Chopra, S.K. Jain, S.P. Srivas-
tava, A.K. Bhatnagar, ‘Hydrocarbon Characterization of
Hydrocracked Base Stocks by One- and Two-Dimensional
NMR Spectroscopy’, Fuel, 75(4), 483–490 (1996).
20. G. Kapur, ‘Determination of Aromatics and Naphthenes
in Straight Run Gasoline by 1 H NMR Spectroscopy. Part
I’, Fuel, 79(9), 1023–1029 (2000).
21. T.M. Shea, S. Gunsel, ‘Modeling Base oil Properties Using
NMR Spectroscopy and Neural Networks’, Tribol. Trans.,
46(3), 296–302 (2003).
22. B.L. Papke, P.N. Tutunjian, ‘Applications of 13 C NMR to
Predict Low Temperature Viscosity Performance of Base
Oils’, Tribotest, 12(3), 211–222 (2006).
23. F. Lima, M. Araújo, L. Borges, ‘Determination of Lubri-
cant Base oil Properties by Near Infrared Spectroscopy
Using Different Sample and Variable Selection Methods’,
J. Near Infrared Spectrosc., 12(1), 159 (2004).
24. R. Palani, A. AbdulGani, N. Balasubramanian, ‘Treatment
of Tannery Effluent Using a Rotating Disc Electrochemical
Reactor’, Water Environ. Res., 89(1), 77–85 (2017).
25. M.H. No, E. Kim, J.S. Lee, H. Jung, ‘Hydrocarbon
Compound Type Analysis of Lube Base oil by GC-MSD:
Advantages on Replacement of the AGHIS Magnetic
Sector Type Mass Spectrometer’, Energy Fuels, 21(6),
3341–3345 (2007).
26. J. Wolska, B. Vrebos, P. Brouwer, S. Dean, ‘Analysis of
Fuels, Lubricants, and Greases Using X-Ray Fluorescence
Spectrometry’, J. ASTM Int., 3(1), 12972 (2006).
27. N. Hourani, H. Muller, F.M. Adam, S.K. Panda, M. Witt,
A.A. Al-Hajji, S.M. Sarathy, ‘Structural Level Character-
ization of Base Oils Using Advanced Analytical Tech-
niques’, Energy Fuel, 29(5), 2962–2970 (2015).
28. J.J. Espada, B. Coto, J.L. Peña, ‘Compositional and Struc-
tural Analysis of Lubricating Oil Feedstock Obtained from
a Light Crude Oil’, Energy Fuel, 23(2), 888–893 (2009).
29. F.C.-Y. Wang, L. Zhang, ‘Chemical Composition of
Group II Lubricant Oil Studied by High-Resolution Gas
Chromatography and Comprehensive Two-Dimensional
Gas Chromatography’, Energy Fuel, 21(6), 3477–3483
(2007).