CHAPTER

4
NAPHTHA

4.1. INTRODUCTION

Naphtha is a liquid petroleum product that boils from about 30C (86F)
to approximately 200C (392F), although there are different grades of
naphtha within this extensive boiling range that have different boiling
ranges (Guthrie, 1967; Goodfellow, 1973; Weissermel and Arpe, 1978;
Francis and Peters, 1980; Hoffman, 1983; Austin, 1984; Chenier, 1992;
Speight, 1999; Hori, 2000). The term petroleum solvent is often used syn-
onymously with naphtha.
On a chemical basis, naphtha is difficult to define precisely because it
can contain varying amounts of its constituents (paraffins, naphthenes, aro-
matics, and olefins) in different proportions, in addition to the potential
isomers of the paraffins that exist in the naphtha boiling range (Tables 4.1
and 4.2). Naphtha is also represented as having a boiling range and carbon
number similar to those of gasoline (Fig. 4.1), being a precursor to
gasoline.
The so-called petroleum ether solvents are specific-boiling-range naphtha
as is ligroin. Thus the term petroleum solvent describes special liquid hydro-
carbon fractions obtained from naphtha and used in industrial processes
and formulations (Weissermel and Arpe, 1978). These fractions are also
referred to as industrial naphtha. Other solvents include white spirit,
which is subdivided into industrial spirit [distilling between 30C and 200C
(86F392F)] and white spirit [light oil with a distillation range of 135C
200C (275F392F)]. The special value of naphtha as a solvent lies in its
stability and purity.
In this chapter, references to the various test methods dedicated to
the determination of the amounts of carbon, hydrogen, and nitrogen
(ASTM D-5291) as well as the determination of oxygen, sulfur, metals,
and elements such as chlorine (ASTM D-808) are not included. Such
tests might be deemed necessary but, in light of the various tests avail-
able for composition, are presumed to be at the discretion of the analyst.
References to the various test methods are presented elsewhere
(Chapter 2).
85
86 naphtha

Table 4.1. General Summary of Product Types and Distillation Range

Product Lower Upper Lower Upper Lower Upper
Carbon Carbon Boiling Boiling Boiling Boiling
Limit Limit Point Point Point Point
C C F F
Refinery gas C1 C4 -161 -1 -259 31
Liquefied petroleum gas C3 C4 -42 -1 -44 31
Naphtha C5 C17 36 302 97 575
Gasoline C4 C12 -1 216 31 421
Kerosene/diesel fuel C8 C18 126 258 302 575
Aviation turbine fuel C8 C16 126 287 302 548
Fuel oil C12 >C20 216 421 >343 >649
Lubricating oil >C20 >343 >649
Wax C17 >C20 302 >343 575 >649
Asphalt >C20 >343 >649
Coke >C50* >1000* >1832*
* Carbon number and boiling point difficult to assess; inserted for illustrative purposes only.

Table 4.2. Increase in the Number of Isomers With

Carbon Number
Carbon Atoms Number of Isomers
1 1
2 1
3 1
4 2
5 3
6 5
7 9
8 18
9 35
10 75
15 4,347
20 366,319
25 36,797,588
30 4,111,846,763
40 62,491,178,805,831

4.2. PRODUCTION AND PROPERTIES

Naphtha is produced by any one of several methods, which include (1) frac-
tionation of straight-run, cracked, and reforming distillates or even frac-
tionation of crude petroleum; (2) solvent extraction; (3) hydrogenation of
 production and properties 87

Figure 4.1. Boiling point and carbon number for various hydrocarbons and petroleum products

cracked distillates; (4) polymerization of unsaturated compounds (olefins);

and (5) alkylation processes. In fact, naphtha may be a combination of
product streams from more than one of these processes.
The more common method of naphtha preparation is distillation.
Depending on the design of the distillation unit, either one or two naphtha
steams may be produced: (1) a single naphtha with an end point of about
205C (400F) and similar to straight-run gasoline or (2) this same fraction
divided into a light naphtha and a heavy naphtha. The end point of the light
naphtha is varied to suit the subsequent subdivision of the naphtha into
narrower boiling fractions and may be of the order of 120C (250F).
Sulfur compounds are most commonly removed or converted to a harm-
less form by chemical treatment with lye, Doctor solution, copper chloride,
88 naphtha

or similar treating agents (Speight, 1999). Hydrorefining processes (Speight,

1999) are also often used in place of chemical treatment. When used as a
solvent, naphtha is selected for low sulfur content, and the usual treatment
processes remove only sulfur compounds. Naphtha with a small aromatic
content has a slight odor, but the aromatics increase the solvent power of
the naphtha and there is no need to remove aromatics unless odor-free
naphtha is specified.
The variety of applications emphasizes the versatility of naphtha. For
example, naphtha is used by paint, printing ink and polish manufacturers
and in the rubber and adhesive industries as well as in the preparation
of edible oils, perfumes, glues, and fats. Further uses are found in the dry-
cleaning, leather, and fur industries and also in the pesticide field. The
characteristics that determine the suitability of naphtha for a particular
use are volatility, solvent properties (dissolving power), purity, and odor
(generally, the lack thereof).
To meet the demands of a variety of uses, certain basic naphtha grades are
produced that are identified by boiling range.The complete range of naphtha
solvents may be divided, for convenience, into four general categories:

1. Special boiling point spirits having overall distillation range within the
limits of 30165C (86329F);
2. Pure aromatic compounds such as benzene, toluene, xylenes, or
mixtures (BTX) thereof;
3. White spirit, also known as mineral spirit and naphtha, usually boiling
within 150210C (302410F);
4. High-boiling petroleum fractions boiling within the limits of 160
325C (320617F).

Because the end use dictates the required composition of naphtha, most
grades are available in both high- and low-solvency categories and the
various text methods can have major significance in some applications and
lesser significance in others. Hence the application and significance of tests
must be considered in the light of the proposed end use.
Odor is particularly important because, unlike most other petroleum
liquids, many of the manufactured products containing naphtha are used in
confined spaces, in factory workshops, and in the home.

4.3. TEST METHODS

Because of the high standards set for naphtha (McCann, 1998) it is essen-
tial to employ the correct techniques when taking samples for testing
 test methods 89

(ASTM D-270, ASTM D-4057, IP 51). Mishandling, or the slightest trace of

contaminant, can give rise to misleading results. Special care is necessary to
ensure that containers are scrupulously clean and free from odor. Samples
should be taken with the minimum of disturbance so as to avoid loss of
volatile components; in the case of low-boiling naphtha it may be necessary
to chill the sample.And, while awaiting examination samples should be kept
in a cool dark place so as to ensure that they do not lose volatile constituents
or discolor and develop odors because of oxidation.
The physical properties of naphtha depend on the hydrocarbon types
present, in general the aromatic hydrocarbons having the highest solvent
power and the straight-chain aliphatic compounds the lowest. The solvent
properties can be assessed by estimating the amount of the various hydro-
carbon types present. This method provides an indication of the solvent
power of the naphtha on the basis that aromatic constituents and naph-
thenic constituents provide dissolving ability that paraffinic constituents
do not. Another method for assessing the solvent properties of naphtha
measures the performance of the fraction when used as a solvent under
specified conditions such as, for example, by the kauri-butanol test method
(ASTM D-l133). Another method involves measurement of the surface
tension from which the solubility parameter is calculated and then pro-
vides an indication of dissolving power and compatibility. Such calcula-
tions have been used to determine the yield of asphaltenes from petroleum
by use of various solvents (Mitchell and Speight, 1973; Speight, 1999;
Speight, 2001). A similar principle is applied to determine the amount of
insoluble material in lubricating oil using n-pentane (ASTM D-893, ASTM
D-4055).
Insoluble constituents in lubricating oil can cause wear that can lead to
equipment failure. Pentane-insoluble materials can include oil-insoluble
materials and some oil-insoluble resinous matter originating from oil or
additive degradation or both. Toluene-insoluble constituents arise from
external contamination, fuel carbon, and highly carbonized materials from
degradation of fuel, oil, and additives or engine wear and corrosion mate-
rials.A significant change in pentane- or toluene-insoluble constituents indi-
cates a change in oil properties that could lead to machinery failure. The
insoluble constituents measured can also assist in evaluating the perform-
ance characteristics of a used oil or in determining the cause of equipment
failure.
Thus one test (ASTM D-893) covers the determination of pentane-
and toluene-insoluble constituents in used lubricating oils with pentane
dilution and centrifugation as the method of separation. The other
test (ASTM D-4055) uses pentane dilution followed by membrane filtra-
tion to remove insoluble constituents that have a size greater than
0.8 mm.
90 naphtha

4.3.1. Aniline Point and Mixed Aniline Point

The test method for the determination of aniline point and mixed aniline
point of hydrocarbon solvents (ASTM D-611, IP 2) is a means for deter-
mining the solvent power of naphtha by estimating of the relative amounts
of the various hydrocarbon constituents. It is a more precise technique than
the method for kauri-butanol number (ASTM D-1133).
The aniline (or mixed aniline) (ASTM D-611, IP 2) point helps in char-
acterization of pure hydrocarbons and in their mixtures and is most often
used to estimate the aromatic content of naphtha. Aromatic compounds
exhibit the lowest aniline points and paraffin compounds have the highest
aniline points, with cycloparaffins (naphthenes) and olefins having aniline
points between the two extremes. In any homologous series the aniline
point increases with increasing molecular weight.
There are five submethods in the test (ASTM D-611, IP 2) for the deter-
mination of the aniline point: (1) Method A is used for transparent samples
with an initial boiling point above room temperature and where the aniline
point is below the bubble point and above the solidification point of the
aniline-sample mixture; (2) method B, a thin-film method, is suitable for
samples too dark for testing by method A; (3) methods C and D are used
when there is the potential for sample vaporization at the aniline point; (4)
method D is particularly suitable where only small quantities of sample are
available; and (5) method E uses an automatic apparatus suitable for the
range covered by methods A and B.
The results obtained by the kauri-butanol test (ASTM D-1133) depend
on factors other than solvent power and are specific to the solute employed.
For this reason, the aniline point is often preferred to the kauri-butanol
number.

4.3.2. Composition

The number of potential hydrocarbon isomers in the naphtha boiling range

(Tables 4.1 and 4.2) renders complete speciation of individual hydrocarbons
impossible for the naphtha distillation range, and methods are used that
identify the hydrocarbon types as chemical groups rather than as individ-
ual constituents.
The data from the density (specific gravity) test method (ASTM D-1298,
IP 160) provides a means of identification of a grade of naphtha but is not
a guarantee of composition and can only be used to indicate evaluate
product composition or quality when used in conjunction with the data
from other test methods. Density data are used primarily to convert
naphtha volume to a weight basis, a requirement in many of the industries
concerned. For the necessary temperature corrections and also for volume
 test methods 91

corrections the appropriate sections of the petroleum measurement tables

(ASTM D-l250, IP 200) are used.
The first level of compositional information is group-type totals as
deduced by adsorption chromatography (ASTM D-1319, IP 156) to give
volume percentage of saturates, olefins, and aromatics in materials that boil
below 315C (600F).
In this test method, a small amount of sample is introduced into a glass
adsorption column packed with activated silica gel, of which a small layer
contains a mixture of fluorescent dyes. When the sample has been adsorbed
on the gel, alcohol is added to desorb the sample down the column and the
hydrocarbon constituents are separated according to their affinities into
three types (aromatics, olefins, and saturates). The fluorescent dyes also
react selectively with the hydrocarbon types and make the boundary zones
visible under ultraviolet light. The volume percentage of each hydrocarbon
type is calculated from the length of each zone in the column.
Other test methods are available. Content of benzene and other aro-
matics may be estimated by spectrophotometric analysis (ASTM D-1017)
and also by gas-liquid chromatography (ASTM D-2267, ASTM D-2600, IP
262). However, two test methods based on the adsorption concept (ASTM
D-2007, ASTM D-2549) are used for classifying oil samples of initial boiling
point of at least 200C (392F) into the hydrocarbon types of polar com-
pounds, aromatics, and saturates and recovery of representative fractions
of these types. Such methods are unsuitable for the majority of naphtha
samples because of volatility constraints.
An indication of naphtha composition may also be obtained from the
determination of aniline point (ASTM D-1012, IP 2), freezing point (ASTM
D-852, ASTM D-1015, ASTM D-1493) (Fig. 4.2), cloud point (ASTM D-
2500) (Fig. 4.3), and solidification point (ASTM D-1493). And, although
refinery treatment should ensure no alkalinity and acidity (ASTM D-847,
ASTM D-1093, ASTM D-1613, ASTM D-2896, IP 1) and no olefins present,
the relevant tests using bromine number (ASTM D-875, ASTM D-1159, IP
130), bromine index (ASTM D-2710), and flame ionization absorption
(ASTM D-1319, IP 156) are necessary to ensure low levels (at the
maximum) of hydrogen sulfide (ASTM D-853) as well as the sulfur com-
pounds in general (ASTM D-l30, ASTM D-849, ASTM D-1266, ASTM D-
2324, ASTM D-3120, ASTM D-4045, ASTM D-6212, IP 107, IP 154) and
especially corrosive sulfur compounds such as are determined by the
Doctor test method (ASTM D-4952, IP 30).
Aromatic content is a key property of low-boiling distillates such as
naphtha and gasoline because the aromatic constituents influence a variety
of properties including boiling range (ASTM D-86, IP 123), viscosity
(ASTM D-88, ASTM D-445, ASTM D-2161, IP 71), stability (ASTM D-525,
IP 40), and compatibility (ASTM D-1133) with a variety of solutes.
92 naphtha

Figure 4.2. Freezing point apparatus for use in the depression of the freezing point of
benzene test

Existing methods use physical measurements and require suitable stan-

dards. Tests such as aniline point (ASTM D-611) and kauri-butanol number
(ASTM D-1133) are of a somewhat empirical nature and can serve a useful
function as control tests. Naphtha composition, however, is monitored
mainly by gas chromatography, and although most of the methods may have
been developed for gasoline (ASTM D-2427, ASTM D-6296), the applica-
bility of the methods to naphtha is sound.
A multidimensional gas chromatographic method (ASTM D-5443)
provides for the determination of paraffins, naphthenes, and aromatics by
carbon number in low olefinic hydrocarbon streams having final boiling
points lower than 200C (392F). In this method, the sample is injected into
a gas chromatographic system that contains a series of columns and switch-
ing values. First a polar column retains polar aromatic compounds, binaph-
thenes, and high-boiling paraffins and naphthenes. The eluant from this
column goes through a platinum column that hydrogenates olefins and then
to a molecular sieve column that performs a carbon number separation
based on the molecular structure, that is, naphthenes and paraffins. The frac-
tion remaining on the polar column is further divided into three separate
 test methods 93

Thermometer

Test jar
Bath

Jacket

Cork caskets

Figure 4.3. Apparatus for the determination of cloud point and pour point

fractions that are then separated on a nonpolar column by boiling point. A

flame ionization detector detects eluting compounds.
In another method (ASTM D-4420) for the determination of the amount
of aromatic constituents, a two-column chromatographic system connected
to a dual-filament thermal conductivity detector (or two single-filament
detectors) is used. The sample is injected into the column containing a polar
liquid phase. The nonaromatics are directed to the reference side of the
detector and vented to the atmosphere as they elute. The column is back-
flushed immediately before the elution of benzene, and the aromatic
portion is directed into the second column containing a nonpolar liquid
phase. The aromatic components elute in the order of their boiling points
and are detected on the analytical side of the detector. Quantitation is
achieved by utilizing peak factors obtained from the analysis of a sample
having a known aromatic content.
Other methods for the determination of aromatics in naphtha include a
method (ASTM D-5580) using a flame ionization detector and methods in
94 naphtha

which a combination of gas chromatography and Fourier transform infrared

spectroscopy (GC-FTIR) (ASTM D-5986) and gas chromatography and
mass spectrometry (GC-MS) (ASTM D-5769) is used.
Hydrocarbon composition is also determined by mass spectrometrya
technique that has seen wide use for hydrocarbon-type analysis of naphtha
and gasoline (ASTM D-2789) as well as identification of hydrocarbon con-
stituents in higher-boiling naphtha fractions (ASTM D-2425).
One method (ASTM D-6379, IP 436) is used to determine the monoaro-
matic and diaromatic hydrocarbon contents in distillates boiling in the
range from 50 to 300C (122572F). In this method the sample is diluted
with an equal volume of hydrocarbon, such as heptane, and a fixed volume
of this solution is injected into a high-performance liquid chromatograph
fitted with a polar column where separation of the aromatic hydrocarbons
from the nonaromatic hydrocarbons occurs. The separation of the aromatic
constituents appears as distinct bands according to ring structure, and a
refractive index detector is used to identify the components as they elute
from the column. The peak areas of the aromatic constituents are compared
with those obtained from previously run calibration standards to calculate
the % w/w monoaromatic hydrocarbon constituents and diaromatic hydro-
carbon constituents in the sample.
Compounds containing sulfur, nitrogen, and oxygen could possibly inter-
fere with the performance of the test. Monoalkenes do not interfere, but
conjugated di- and polyalkenes, if present, may interfere with the test
performance.
Another method (ASTM D-2425) provides more compositional detail
(in terms of molecular species) than chromatographic analysis, and the
hydrocarbon types are classified in terms of a Z-series in which Z (in the
empirical formula CnH2n+Z) is a measure of the hydrogen deficiency of
the compound. This method requires that the sample be separated into
saturate and aromatic fractions before mass spectrometric analysis (ASTM
D-2549), and the separation is applicable to some fractions but not others.
For example, the method is applicable to high-boiling naphtha but not to
low-boiling naphtha because it is impossible to evaporate the solvent used
in the separation without also losing the lower-boiling constituents of the
naphtha under investigation.
The percentage of aromatic hydrogen atoms and aromatic carbon atoms
can be determined by high-resolution nuclear magnetic resonance spec-
troscopy (ASTM D-5292) that gives the mole percent of aromatic hydro-
gen or carbon atoms. Proton (hydrogen) magnetic resonance spectra are
obtained on sample solutions in either chloroform or carbon tetrachloride
with a continuous wave or pulse Fourier transform high-resolution mag-
netic resonance spectrometer. Carbon magnetic resonance spectra are
 test methods 95

obtained on the sample solution in chloroform-d with a pulse Fourier trans-

form high-resolution magnetic resonance.
The data obtained by this method (ASTM D-5292) can be used to eval-
uate changes in aromatic contents in naphtha as well as kerosene, gas oil,
mineral oil, and lubricating oil. However, results from this test are not
equivalent to mass- or volume-percent aromatics determined by the chro-
matographic methods because the chromatographic methods determine the
percent by weight or percent by volume of molecules that have one or more
aromatic rings and alkyl substituents on the rings will contribute to the
percentage of aromatics determined by chromatographic techniques.
Low-resolution nuclear magnetic resonance spectroscopy can also be
used to determine percent by weight hydrogen in jet fuel (ASTM D-3701)
and in light distillate, middle distillate, and gas oil (ASTM D-4808). As
noted above, chromatographic methods are not applicable to naphtha
where losses can occur by evaporation.
The nature of the uses found for naphtha demands compatibility with
the many other materials employed in formulation, waxes, pigments, resins,
etc.; thus the solvent properties of a given fraction must be carefully meas-
ured and controlled. For most purposes volatility is important, and, because
of the wide use of naphtha in industrial and recovery plants, information
on some other fundamental characteristics is required for plant design.
Although the focus of many tests is analysis of the hydrocarbon
constituents of naphtha and other petroleum fractions, heteroatoms
compounds that contain sulfur and nitrogen atoms cannot be ignored
and methods for their determination are available. The combination of gas
chromatography with element-selective detection gives information about
the distribution of the element. In addition, many individual heteroatomic
compounds can be determined.
Nitrogen compounds in middle distillates can be selectively detected by
chemiluminescence. Individual nitrogen compounds can be detected down
to 100 ppb nitrogen. Gas chromatography with either sulfur chemilumi-
nescence detection or atomic emission detection has been used for sulfur
selective detection.
Estimates of the purity of these products are determined in laboratories
with a variety of procedures such as freezing point, flame ionization
absorbance, ultraviolet absorbance, gas chromatography, and capillary gas
chromatography (ASTM D-850, ASTM D-852, ASTM D-853, ASTM D-
848, ASTM D-849, ASTM D-1015, ASTM D-1016, ASTM D-1078, ASTM
D-1319, ASTM D-2008, ASTM D-22368, ASTM D-2306, ASTM D-2360,
ASTM D-5917, IP 156).
Gas chromatography (GC) has become a primary technique for deter-
mining hydrocarbon impurities in individual aromatic hydrocarbons and
96 naphtha

the composition of mixed aromatic hydrocarbons. Although a measure of

purity by gas chromatography is often sufficient, gas chromatography is not
capable of measuring absolute purity; not all possible impurities will pass
through the gas chromatography column, and not all those that do will be
measured by the detector. Despite some shortcomings, gas chromatography
is a standard, widely used technique and is the basis of many current test
methods for aromatic hydrocarbons (ASTM D-2306 ASTM D-2360, ASTM
D-3054, ASTM D-3750, ASTM D-3797, ASTM D-3798, ASTM D-4492,
ASTM D-4534, ASTM D-4735, ASTM D-5060, ASTM D-5135, ASTM D-
5713, ASTM D-5917, ASTM D-6144).
When classes of hydrocarbons, such as olefins, need to be measured, tech-
niques such as bromine index are used (ASTM D-1492, ASTM D-5776).
Impurities other than hydrocarbons are of concern in the petroleum
industry. For example, many catalytic processes are sensitive to sulfur con-
taminants. Consequently, there is also a series of methods to determine
trace concentrations of sulfur-containing compounds (ASTM D-1685,
ASTM D-3961, ASTM D-4045, ASTM D-4735).
Chloride-containing impurities are determined by various test methods
(ASTM D-5194, ASTM D-5808, ASTM D-6069) that have sensitivity to 1
mg/kg, reflecting the needs of industry to determine very low levels of these
contaminants.
Water is a contaminant in naphtha and should be measured using the
Karl Fischer method (ASTM E-203, ASTM D-1364, ASTM D-1744, ASTM
D-4377, ASTM D-4928, ASTM D-6304), by distillation (ASTM D-4006), or
by centrifugation (ASTM D-96) and excluded by relevant drying methods.
Tests should also be carried out for sediment if the naphtha has been
subjected to events (such as oxidation) that could lead to sediment forma-
tion and instability of the naphtha and the resulting products. Test methods
are available for the determination of sediment by extraction (ASTM
D-473, IP 285) or by membrane filtration (ASTM D-4807, IP 286) and the
determination of sediment simultaneously with water by centrifugation
(ASTM D-96, ASTM D-1796, ASTM D-2709, ASTM D-4007, IP 373, IP
374).

4.3.3. Correlative Methods

Correlative methods have long been used as a way of dealing with the com-
plexity of various petroleum fractions, including naphtha. Relatively easy
to measure physical properties such as density (or specific gravity) (ASTM
D-2935 ASTM D-3505, ASTM D-4052) are also required. Viscosity (ASTM
D-88, ASTM D-445, ASTM D-2161, IP 71), density (ASTM D-287,
ASTM D-891, ASTM D-941, ASTM D-1217, ASTM D-1298, ASTM D-
1555, ASTM D-1657, ASTM D-2935, ASTM D-4052, ASTM D-5002, IP 160,
 test methods 97

Table 4.3. Refractive Index of Selected Hydrocarbons

Compound Refractive Index n20
D

n-Pentane 1.3578
n-Hexane 1.3750
n-Hexadecane 1.4340
Cyclopentane 1.4065
Cyclopentene 1.4224
Pentene-1 1.3714
1,3-Pentadiene 1.4309
Benzene 1.5011
cis-Decahydronaphthalene 1.4814
Methylnaphthalenes 1.6150

Table 4.4. Physical Properties of Selected Petroleum Products

Refractive Specific Viscosity, cSt Molecular
Index nD20 Gravity 60/60F Weight
100F 210F
1.5185 0.9250 26.35 3.87 300
1.4637 0.8406 14.55 3.28 353
1.5276 0.9367 1955.00 49.50 646
1.4799 0.8724 3597.00 27.35 822

IP 235, IP 365), and refractive index (ASTM D-1218) have been correlated
to hydrocarbon composition (Tables 4.3 and 4.4).

4.3.4. Density (Specific Gravity)

Density (the mass of liquid per unit volume at 15C) and the related
terms specific gravity (the ratio of the mass of a given volume of liquid at
15C to the mass of an equal volume of pure water at the same tempera-
ture) and relative density (same as specific gravity) are important proper-
ties of petroleum products as they are a part of product sales specifications,
although they only play a minor role in studies of product composition.
Usually a hydrometer, pycnometer, or digital density meter is used for the
determination in all these standards.
The determination of density (specific gravity) (ASTM D-287, ASTM D-
891, ASTM D-941, ASTM D-1217, ASTM D-1298, ASTM D-1555, ASTM
D-1657, ASTM D-2935, ASTM D-4052, ASTM D-5002, IP 160, IP 235, IP
365) (Fig. 4.4) provides a check on the uniformity of the naphtha and
permits calculation of the weight per gallon. The temperature at which the
98 naphtha

Figure 4.4. Density weighing bottle

determination is carried out and for which the calculations are to be made
should also be known (ASTM D-1086). However, the methods are subject
to vapor pressure constraints and are used with appropriate precautions to
prevent vapor loss during sample handling and density measurement. In
addition, some test methods should not be applied if the samples are so
dark in color that the absence of air bubbles in the sample cell cannot be
established with certainty. The presence of such bubbles can have serious
consequences for the reliability of the test data.

4.3.5. Evaporation Rate

The evaporation rate is an important property of naphtha, and although

there is a significant relation between distillation range and evaporation
rate, the relationship is not straightforward.
A simple procedure for determining the evaporation rate involves use
of at least a pair of tared shallow containers, each containing a weighed
amount of naphtha. The cover-free containers are placed in a temperature-
and humidity-controlled draft-free area. The containers are reweighed at
intervals until the samples have completely evaporated or have left a
 test methods 99

residue that does not evaporate further (ASTM D-381, ASTM D-1353,
IP 131).
The evaporation rate can be derived either (1) by a plot of time versus
weight using a solvent having a known evaporation rate for comparison or
(2) from the distillation profile (ASTM D-86, IP 123).

4.3.6. Flash Point

The flash point is the lowest temperature at atmospheric pressure (760

mmHg, 101.3 kPa) at which application of a test flame will cause the vapor
of a sample to ignite under specified test conditions. The sample is deemed
to have reached the flash point when a large flame appears and instanta-
neously propagates itself over the surface of the sample. Flash point data
are used in shipping and safety regulations to define flammable and com-
bustible materials. Flash point data can also indicate the possible presence
of highly volatile and flammable constituents in a relatively nonvolatile or
nonflammable material.
Of the available test methods, the most common method of determining
the flash point confines the vapor (closed cup method) until the instant the
flame is applied (ASTM D-56, ASTM D-93, ASTM D-3828, 6450, IP 34, IP
94, IP 303) (Fig. 4.5). An alternate method that does not confine the vapor

Figure 4.5. Pensky-Martens flash point apparatus (ASTM D-56)

100 naphtha

(open cup method) (ASTM D-92, ASTM D-1310, IP 36) gives slightly
higher values of the flash point.
Erroneously high flash points can be obtained when precautions are not
taken to avoid the loss of volatile material. Samples should not be stored
in plastic bottles, because the volatile material may diffuse through the walls
of the container. The containers should not be opened unnecessarily. The
samples should not be transferred between containers unless the sample
temperature is at least 20F (11C) below the expected flash point.
Another test (ASTM E-659) that can be used as a complement to the
flash point test involves determination of the auto-ignition temperature.
However, the flash point should not be confused with auto-ignition tem-
perature, which measures spontaneous combustion with no external source
of ignition.

4.3.7. Kauri-Butanol Value

The kauri-butanol value (ASTM D-1133) is the number of milliliters of the

solvent, at 15C (77F), required to produce a defined degree of turbidity
when added to 20 g of a standard solution of gum kauri resin in n-butyl
alcohol. The kauri-butanol value of naphtha is used to determine relative
solvent power.
For kauri-butanol values of 60 and higher, the standard is toluene, which
has an assigned value of 105, whereas for kauri-butanol values less than 60,
the standard is a blend of 75% n-heptane and 25% toluene, which has an
assigned value of 40. The kauri-butanol value of products that are classified
as regular mineral spirits normally varies between 34 and 44; xylene is 93,
and aromatic naphtha falls in the range 55108.
However, the data obtained by the kauri-butanol test depend on factors
other than solvent power and are specific to the solute used. For this reason,
the aniline point is often preferred to the kauri-butanol number.

4.3.8. Odor and Color

The degree of purity of naphtha is an important aspect of naphtha proper-

ties, and strict segregation of all distribution equipment is maintained to
ensure strict and uniform specification for the product handled. Naphtha is
refined to a low level of odor to meet the specifications for use.
In general the paraffinic hydrocarbons possess the mildest odor and the
aromatics the strongest, the odor level (ASTM D-268, ASTM D-1296, IP
89) being related to the chemical character and volatility of the constituents.
Odors caused by the presence of sulfur compounds or unsaturated con-
stituents are excluded by specification. And apart from certain high-boiling
aromatic fractions, which are usually excluded by volatility from the major-
 test methods 101

ity of the naphtha fractions, which may be pale yellow in color, naphtha is
usually colorless (water white).
Measurement of color (ASTM D-l56, ASTM D-848, ASTM D-1209,
ASTM D-1555, ASTM D-5386, IP 17) provides a rapid method of check-
ing the degree of freedom from contamination. Observation of the test for
residue on evaporation (ASTM D-381, ASTM D-1353, IP 131) provides a
further guard against adventitious contamination.

4.3.9. Volatility

Distillation, as a means of determining the boiling range (hence the vola-

tility) of petroleum and petroleum products, has been in use since the
beginning of the petroleum industry and is an important aspect of pro-
duct specifications.
Thus one of the most important physical parameters is the boiling range
distribution (ASTM D-86, ASTM D-1078, ASTM D-2887, ASTM D-2892,
IP 123). The significance of the distillation test is the indication of volatil-
ity, which dictates the evaporation rate, an important property for naphtha
used in coatings and similar applications where the premise is that the
naphtha evaporates over time, leaving the coating applied to the surface.
In the basic test method (ASTM D-86, IP 123) a 100-ml sample is dis-
tilled (manually or automatically) under prescribed conditions. Tempera-
tures and volumes of condensate are recorded at regular intervals, from
which the boiling profile is derived.
The determination of the boiling range distribution of distillates such as
naphtha and gasoline by gas chromatography (ASTM D-3710) not only
helps identify the constituents but also facilitates on-line controls at the
refinery. This test method is designed to measure the entire boiling range
of naphtha with either high or low Reid vapor pressure (ASTM D-323, IP
69). In this method, the sample is injected into a gas chromatographic
column that separates hydrocarbons in boiling point order. The column
temperature is raised at a reproducible rate, and the area under the chro-
matogram is recorded throughout the run. Calibration is performed with a
known mixture of hydrocarbons covering the expected boiling range of the
sample.
Another method is described as a method for determining the carbon
number distribution (ASTM D-2887, IP 321), and the data derived by this
test method are essentially equivalent to those obtained by true boiling
point (TBP) distillation (ASTM D-2892). The sample is introduced into a
gas chromatographic column that separates hydrocarbons in boiling point
order. The column temperature is raised at a reproducible rate, and the area
under the chromatogram is recorded throughout the run. Boiling temper-
atures are assigned to the time axis from a calibration curve obtained under
102 naphtha

the same conditions by running a known mixture of hydrocarbons cover-

ing the boiling range expected in the sample. From these data, the boiling
range distribution may be obtained. However, this test method is limited to
samples with a boiling range greater than 55C (100F) and having a vapor
pressure (ASTM D-323, ASTM D-4953, ASTM D-5190, ASTM D-5191,
ASTM D-5482, ASTM D-6377, ASTM D-6378, IP 69, IP 394) sufficiently
low to permit sampling at ambient temperature.
Naphtha grades are often referred to by boiling points, that is, the
defined temperature range in which the fraction distills. The ranges are
determined by standard methods (ASTM D-8, ASTM D-107, IP 123, IP
195), it being especially necessary to use a recognized method because
the initial and final boiling points, which ensure conformity with volatility
requirements and absence of heavy ends, are themselves affected by the
testing procedure.
A simple test for the evaporation properties of naphtha is available
(ASTM D-381, IP 131), but the volatility of naphtha is generally considered
a measure of its drying time in use. And the temperature of use obviously
governs the choice of naphtha. A high- boiling narrow distillation fraction
of gas oil may be required for a heat-set ink, where the operating temper-
ature may be as high as 316C (600F). However, the need for vacuum dis-
tillation (ASTM D-1160) as a product specification in the boiling range of
naphtha is not necessary. By definition, naphtha very rarely has such a high
boiling point.
Although pure hydrocarbons such as pentane, hexane, heptane, benzene,
toluene, and xylene, which are now largely of petroleum origin, may be
characterized by a fixed boiling point, naphtha is a mixture of many hydro-
carbons and cannot be so identified. The distillation test does, however, give
a useful indication of their volatility. The data obtained should include the
initial and final temperatures of distillation together with sufficient tem-
perature and volume observations to permit a characteristic distillation
curve to be drawn.
This information is especially important when a formulation includes
other volatile liquids because the performance of the product will be
affected by the relative volatility of the constituents. An illustration of the
importance of this aspect is found in the use of specifically defined boiling
point naphtha in cellulose lacquers, where a mixture with ester, alcohols,
and other solvents may be employed. The naphtha does not act as a solvent
for the cellulose ester but is incorporated as a diluent to control the vis-
cosity and flow properties of the mixture. If the solvent evaporates too
rapidly blistering and pimpling of the surface coating may result, whereas
if the solvent evaporates unevenly, leaving behind a higher proportion of
the naphtha, precipitation of the cellulose may occur, leading to a milky
opaqueness known as blushing.
 references 103

Although much dependence is placed on the assessment of volatility by

distillation methods, some specifications include measurement of drying
time by evaporation from a filter paper or dish. Laboratory measurements
are expressed as evaporation rate either by reference to a pure compound
evaporated under conditions similar to those for the sample under test or
by constructing a time-weight loss curve under standard conditions.
Although the results obtained on the naphtha provide a useful guide, it is
better, wherever possible, to carry out a performance test on the final
product when assessing formulations.
In choosing naphtha for a particular purpose it is necessary to relate
volatility to the fire hazard associated with its use, storage, and transport
and also with the handling of the products arising from the process. This is
normally based on the characterization of the solvent by flash point limits
(ASTM D-56, ASTM D-93, IP 34, IP 170).

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