Determination of Trace Metals in Petroleum Fractions
J. H. KARCHiiER AND E. L . GUNN
Humble Oil & Rejining Co., Baytown, Tex.
The occurrence of trace metals in petroleum and its
products is of considerable significance to the in-
dustry. To evaluate the influence of a given metal or
its compounds, analytical methods of satisfactory
sensitivity and accuracj must be available for testing
the oil. The time-honored method whereby com-
bustion of the oil is carried out with subsequent
determinations of indhidual components on the ash
residue has certain inherent limitations: the pos-
sible error through loss of ash matter and the exces-
sive time and effort required for the analysis itself.
4 procedure has been developed in which, by rigid
I T H I S recent years, interest of the petroleum industry
in the occurrence of trace metals in various products and
substances associated with the industry has increased markedly.
This interest derives from the association of metals \Tith geologi-
cal origin of crudes, the influence of contaminant metals in refm-
ing or processing of pet,roleum products, or the effects of metals
on utilization or performance characteristics of the finished prod-
ucts. In addition to the organic constituents of petroleum,
of which carbon and hydrogen are the chief elemental components,
oxygen, nitrogen, sulfur, and various naturally occurring inor-
ganic substances are found in trace amounts. Varying concen-
trations of the mineral constituents remain wit,h the oil as it
flows on its devious course through the refinery. In some petro-
leum fractions the amount of metal constituents may be lessened
t~ssentiallyto zero by virtue of the treatment received en route
through the refinery; for other fractions, the amount may be
considerably increased by concentration or by metal pickup
from pipes or storage facilities. The metal content of an oil
alp0 may be enhanced as a consequence of the formation of nietal
soaps of d f o n i r or naphthenic acids in treating processes
PRESESCE OF 3lETALS IN OILS
Influence of Metals. The influence of metals occurring
initially in oils or introduced extraneously in processing or during
service may be illustrated by certain examples. I n fluid catalytic
cracking the presence of only a few pounds of such trace metals
as iron, nickel, and vanadium imparted from the feed stock and
acc*urnu]ated in each ton of catalyst may result in expensive
c,atalyst replacement because of their adverse effects on qualit).
anti distribution of the cracked products (14). Inorganic deposi-
tion products from fuels often give rise to refinery problems in
heat transfer, equipment deterioration, and premature failures.
Metal ernbrittlement, pitting by vanadium compounds, or other
costly corrosive effects often are attributable to trace nietals
rarried by oils ( 7 ) . F'arious chemical reactions of petroleum
ronipounds and their derivatives are believed to be accelerated
h y the presence of trace metals. Lubricant breakdown and engine
wear may be correlated with the identity and concentration of
metals in crankcase oils.
Interest of the petroleum industry in trace metals does not, of
course, stem entirely from debits incurred by the presence
of deleterious metals in oils. On the credit side, properties of
certain petroleum products actually may be greatly enhanced
hy the presence of added metal compounds. Thus, a number of
finished products such as additive-containing heating oils, deter-
gent lubricating oils, leaded gasolines, and inhibitor-containing
blends owe much of their desirable characteristics to the presence
1733
control of sampling and of variables in combustion
and ignition, a reproducibility of about &lo70 in the
ash range of 0.0001 to O.OlC& and &5qc in the range of
0.01 to 0.370 is obtained. Colorimetric and spectro-
scopic methods have proved adequate for determin-
ing individual metals in milligram quantities of ash
substance, the relative precision of these methods
being zk10 to 20%. Spectroscopicmethods providing
an accuracy of zk2O7' also may be applied to the direct
determination of trace metals in certain stocks to
circumvent some of the problems associated with
indirect chemical methods.
of metallic compounds Tyhich purposely are introduced into
them.
States of Metals in Oils. .4 complete identification of the
chemical and physical states or forms of all naturally occurring
trace metals in petroleum is difficult to ascertain. Such informa-
tion would be specifically useful to the industry. In oil explora-
tion, for example, further light would be thrown on the source
and geological origin of crudes, TTere full information on the
physical and chemical forms of trace metals existing in them
available. As another example, a ready method whereby such
forms could be easily defined or identified would provide poten-
tially useful data in designing effective treating processes, should
the removal of objectionable metal contaminants from certain
stocks be deemed desirable.
The physical forms in which metals may exist in oils include
true solutions of organometallic substances, suspended solid
particles in highly divided form, and colloidal or emulsified
dispersions of minute bodies containing metal compounds or
complexes. The coexistence in an oil of trace metals having dif-
ferent physical forms of dispersion or chemical combinationappear
probable; this has been indicated by certain metal-decontamina-
tion studies made in oils. For example, in this laboratory the
percolation of a petroleum residuum over adsorbent gels or acti-
vated carbon was found to be highly effective for the removal of
compounds of iron, sodium, and calcium, ~1hereas compounde of
magnesium, vanadium, and nickel were not removed to any
appreciable extent by the treatment. This suggests that dif-
ferences in selectivity of removal are attributable to differences
in states of division or forms of combination of the respective
metals in the residuum stock. Liquid extraction techniques such
as water washing of gas oils 1%-erefound to be selective in the re-
moval of trace metals; specifically they are most selective for
sodium and other alkaline compounds. Even filtration tech-
nique* may be effective for some stocks in removal of a portion
of the metal contaminants, presumably that portion consisting
of metal-containing aggregates too large to pass the filter pores.
Centrifugation also provides a possible means whereby metal-
containing bodies may be segregated from an oil.
The form of chemical combination of a metal as it occurs in
oils may be classified essentially as organic or inorganic. Inor-
ganic forms include oxides, sulfate., carbonates, chlorides, and
phosphates. Organic forms include metal soaps and chelate-
type organometallic complexes. The separation and identifica-
tion of organometallic forms are somewhat more involved and
difficult than the separation of inorganic forms, but naturally
occurring metal complexes have been separated from oils and
their forms of chemical combination identified. A study on the
identification of metal complexes in Santa Maria Valley, Cali-
1734
fornia, crude has been reported (20) in which comparison of
absorption spectra of extracts of the crude with literature spectra
of pure compounds showed that vanadium is present in the crude
as the porphyrin complex.
Analytical Methods. Determination of the mineral content
of the various petroleum stocks is necessary, so that some measure
of control can be brought to bear to maintain product quality.
Some of the known effects of various minerals on product quality
have been discussed above and current research is seeking to
establish other correlations. In many cases a total mineral con-
tent has been acceptable as a control, whereas in other cases it is
desirable to pinpoint the correlations by identification and deter-
mination of a specific element.
Several methods of determining the mineral content have been
employed. Most common is the ashing procedure in which the
oil is burned and the residue is heated to remove the carbonaceous
material and then weighed. In this type of analysis it is assumed
that all the mineral components are nonvolatile and are not lost
in any way through the burning process. It has been recognized
that not all mineral components are nonvolatile. For example,
in the determination of lead in petroleum stocks the ashing pro-
cedure is modified by the addition of sulfuric acid during the ash-
ing step, so that lead will be retained in the residue as the rela-
tively nonvolatile lead sulfate. Another method of determining
the total metallic constituents in petroleum is by wet oxidation
of the oil in a Kjeldahl-type digestion with hot sulfuric and nitric
acids. This method is usually long and tedious and amounts
of mineral residue are usually small as a consequence of the small
amount of sample that is necessarily used in this oxidation.
Another method of determining the metallic content is byextrac-
tion of the oil with a strong acid. This type of technique has been
used successfully in the determination of lead in gasoline, and has
been investigated as a means of determining metals in other types
of stocks (18). This method is not in so widespread use as is the
ash procedure, presumably because of its lack of versatility and
the incompleteness of the extraction when applied to certain
stocks ( I d ) . The total mineral or metallic content can be ob-
tained by a summation of individual components of an oil. The
individual metallic components can be obtained either by analysis
of the ash obtained on burning the oil or by direct examination
of the oil. If the analysis of individual constituents is undertaken
after the ash is obtained, the subsequent analytical problems
are much like the determination of minerals and rocks, except
for the very small amount of solid materials usually on the order
of about 10 mg. Consequently, conventional gravimetric
procedures cannot be employed. For many minerals colori-
metric procedures have proved satisfactory and a number of these
have been described ( I S , 19, If,22).
The emission spectrograph offers a means of determining the
mineral content directly without prior ashing of the sample (4).
Because of the extreme sensitivity of this instrument to most
metals, only very small amounts of oil are required to make the
determination. I n one method described in the literature (IO)
a small amount of oil is charged to a specially prepared electrode
and the ashing is carried out inside the electrode. The electrode
containing the ash is then placed in the emission spectrograph
and the analysis is obtained in the usual manner. A method of
determining minerals by the use of the spectrograph is discussed
below, wherein it is not necessary to carry out this initial micro-
ashing step, The electrode is dipped into the oil to be analyzed
and sufficient oil is retained on the electrode to carry out the
subsequent determinations of a number of metals simultaneously.
Although each of the procedures for determining the total ash
content has some particular merit, each has certain inherent
weaknesses, which cast suspicion upon the accuracy of the results.
For example, in the ashing technique there is the possibility
that some of the metals are lost by volatilization or by mechanical
entrainment during the burning process; the extraction method
has been shown to be time-consuming and inadequate in some
ANALYTICAL CHEMISTRY
cases; and wet oxidation methods are not practical for routine
determinations. Because emission spectrographic methods and
the ashing procedure offered the least objections, it was decided
to investigate these methods to determine if accurate and reliable
determinations could be obtained.
INVESTIGATIONAL WORK ON ASHING PROCEDURE
In order to determine the extent to which ashing can be relied
upon to give accurate results for the total mineral determination
and for use as a preliminary step in the determination of individual
metals in an oil, it was necessary t o investigate the following:
1. Stratification of sample on standing.
2. Possible losses through volatilization of inorganic constitu-
ents.
3. Possible losses through mechanical entrainment during the
burning of the oil.
4. Size of sample.
Prom this investigational work, which is subsequently discussed
in detail, a modified ashing procedure was developed; the pro-
cedural steps are described and the accuracy and reproducibility
of the method are evaluated.
Table I. Stratification of Samples i n Gallon Glass Bottles
(Petrolatum samples stored in oven)
Ash Content, Weight %
Sampled Sampled from
according to t o p after standing
Sample procedurea 8 weeksb Deviation, %
a Average of six determinations.
b Average of two determinations.
Stratification of Samples in Containers. The inorganic com-
ponents of an oil may be present in solution or as solids in suspen-
sion. The particle size of the solids is not known. It was SUS-
pected that erratic answers could be obtained upon ashing the
samples if care were not exercised in sampling the oil. In order
to determine the effect of stratification of samples in containers
upon the accuracy of the ash procedure, five plant samples were
analyzed for ash contents immediately after receipt and after
standing for 8 weeks without agitation. In Table I are shown
some results obtained on samples as received and on portions
withdrawn from the top of each sample (contained in a gallon
bottle) after standing for 8 weeks. Negligible differences in
ash contents were obtained on three of the samples, while two
of the samples showed a substantial reduction in ash content on
standing. Although these data show that not all samples are
affected by settling, they demonstrate that stratification does
affect the results obtained on certain samples. Consequently,
it was believed advisable to incorporate in any revised procedure
a provision that all of the sample in the container be removed for
the analysis. This, together with the added stipulation that the
containers are to be washed with xylene and the washings added
to the original sample, would be likely to eliminate any errors
due t o possible stratification.
Ash Volatilization. POSSIBLELOSSES DURING IGNITION.
To determine the importance of this factor upon the accuracy
of the ash determination, a plant sample was first ignited in a
muffle oven to a constant weight for 2 hours a t 1150' F., the
temperature was then raised in two steps and the sample re-
weighed after it had attained a constant weight a t each tempera-
ture.
Temperature, O F. Ash, Wt. %
'
1150 0.0086
1500 0.0035
1800 0.0006
Temperature had a very profound effect upon the measured
V O L U M E 24, NO. 11, N O V E M B E R 1 9 5 2 1735
--
burned create a larger volume of gas than the volume of olygen
Table 11. Volatilit? of Sodium Chloride at Various consumed, This is shown in the following equation:
Temperatures
(25 ing of sample employed) C,H, +( +
TL
3
- 0 2 = nCO2 + H20
Time of Heat, Hours
' ' lo 2o The number of moles of gas on the left side of the equation is
Temp
.^^^
LVVU
1' Weight c& Loss after Heating
.. --
8.'"
n + x/4 while on the right side it is n +
x/2, which represents a
1150 2,'O 2:s 2,'s $.'O 4:0 8'0 10.0 slight increase in volume. Thus the amount'of gas in the muffle
1300
1500 316.0
0 64 8.0 14.5 2
0 8 4 . 0 88.0 994 . 0
0 44.0
.. .. .. ::. . is greater than that which would be accounted for by leaks alone.
1800 99.5 .. .. . .. .. .. ,. .. INFLUESCE OF SULFATION.A series of experiments \vas
a IO-my. sample instead of 2 3 mg. conducted t o determine whether volatilization losses could be
reduced by converting the sodium chloride in the original sample
t o sodium sulfate, through treatment with sulfuric acid, before
ash content of this particular sample. Tests conducted upon a igniting the sample. The data in Table IV show that negligible
water extract, obt,ained from another portion of this sample volatilization of sodium sulfate occurred after 20 hours at
sholyed that the soluble portion of the ash consisted principally temperatures as high as 1300"F., and that only 2.4 weight 7 0 is lost
of sodium chloride. Sodium chloride was therefore selected as through volatilization a t 1800" F. Although it is obvious that
a tl-pica1 inorganic material for study because it is perhaps more errors caused by volatilization of sodium chloride could be essen-
volatile than the majority of t,he other inorganic materials com- tially eliminated hy converting the chloride to sulfate, this
monly occurring in oils. Although the vapor pressure of sodium technique has the disadvantages that (1) it is necessary to carry
chloride has been established, its rate of volatilization can be out the additional step of adding sulfuric acid and carefully
influenced by the shape of the dish, the volume of the muffle fuming it off, and (2) erroneously high results will be obtained
furnace, and the rat,e at which the air is displaced from the fur- for the weight per cent ash if the chloride is converted t o the
nace. Consequently, a series of experiments was conducted to sulfate. Hon-ever, iron (and other related metals) compounds
determine the effect of temperature upon volatilization of sodium in the ash would not be affected by sulfating, since the subse-
chloride xhen using the same equipment that was ordinarily used quent ignition temperature of 1800' F would be sufficiently high
for the ashing determination. This equipment is perhaps typical t o convert the ferric sulfate back t o ferric ocide.
of that commonly found in manj- refinery laboratories.
I n Table I1 are shown results obtained when 25-mg. (and 10-
mg,) samples of sodium chloride \yere heated from 0.5 t o 24 hours Table 111. Average Number of Air Displacements from
a t temperatures ranging from 1000" t o 1800" F. Essentially Muffle Furnace per Hour
all of the sodium chloride had volatilized within 0.5 hour at Period of Average
Measurement, Displacement
1800'F., and only about 4% of the sodium chloride \vas lost Temp., 17. Hours per Hour
through volatilizaiion after -1 hours at 1150' F. Because periods 1000 24 0 7
as long as 7 hours may be required to remove all of the carbon 1150 16 1 1
1300 20 1.3
in a sample when the temperature is as IOK as 1150' F., and the I500 2 1.9
loss of sodium chloride through voiat'ilization may be appreciable
over extended periods of time, even at 1150' F., it was deemed Table IV. Volatility of Sodium Sulfate
advisable t o conduct the ignition at a temperature of about (200-nig. soinple employed. Samples previously dried 1 hour a t 212' F.)
1000" F. A 10-mg. sample of sodium chloride lost only 8% Time of H e a t , Hours
through volatilization after 24 hours at 1000" F. 0.5 1.0 2 0 4 0 5.0 20.0
From the volume of the muffle furnace, which may be computed T e m p . , ' F, Weight %' Loss after Heating
from the dimensions of 5.25 inches wide by 3.75 inches high by 11 1150 0 0 0 1 0 0 0 2 0 2 0 0
1300 0 0 +01 +03 f O 2 0 0 0 2
inches deep, and the vapor pressure of the sodium chloride a t a 1800 0 5 0 8 1 0 1 1 1 2 2 4
given temperature, the weight of sodium chloride present as a
gas in the muffle oven can be coniputcd. assuming that the perfect
gas l a w hold. This value can he compared to t'he actual losses The validity of the conclusions concerning the volatility of the
of sodium chloride shoxvn in Table I1 for the respective tempera- sodium chloride and the ferric oxide was demonstrated using a
tures. The actual loss divided hy the theoretical weight of series of synthetic samples which were prepared by adding t o an
sodium chloride required t o saturate the gaseous volume of the oil of an extremely IOIT ash content known amounts of sodium
muffle a t a given temperature gives a rough indication of the chloride and ferric oxide. The results, shown in Table V, indi-
number of times the air in the muffle was displaced. This value cate that all the sodium chloride was lost completely after 1
divided by the number of hours the sample was maintained at the hour at 1800" F., while essentially all the ferric oxide was recov-
temperature gives an average air displacement value per hour. ered. In those cases Tvhere the samples were sulfated, the
In this manner the valurs shown in Table I11 vere obtained. calculated amounts of sodium sulfate plus ferric oxide were
The average displacement per hour increases x i t h increasing obtained. An accuracy of about 401, map. obtained.
temperature, -4lthough the reason for this is not fully under- It mal- be possible t o utilize this technique of sulfating the
stood, this effect may be partially explained by the fact that as ash for determining volatile alkaline salts. This could be
the temperature increases the density of the gas decreases, thus accomplished by sulfating a portion of a sample and igniting
creating a greater pressure differential. both the sulfated and the nonsulfated samples at 1800" F. for
These values offer means of roughly approximating how much about 1 hour. Because essentially all of the alkaline chlorides
of a given inorganic material will be lost through volatilization and none of the alkaline sulfates will volatilize under these condi-
a t a given temperature, from a knowledge of its vapor pressure. tions, the weight per cent of the alkaline chlorides in the sample
(hlthough these values are characteristic of the particular could be determined from the difference in weight of the two
furnace used in this study, the values for other furnaces of like samples after the ignition by applying the appropriate conversion
size and design would probably be similar.) In actual ashing factors. The results in Table V illustrate this technique.
it should be anticipated that the volatilization loss per hour for Losses by Mechanical Entrainment. Mechanical entrainment
the initial few hours ma)- be somewhat higher than indicated, losses are those sustained when minute particles of the ash are
owing to t'he presence of carhonaceous materials which when carried upward in the flame by the rising heat current and out of
1736 ANALYTICAL CHEMISTRY
blend was increased. However, the data as shown in Table VI1
Table V. Results of Ashing Sulfated and Vnsulfated Oil indicate that the ash values of the blends calculated from the com-
of Know-n Ash Content at Final Ignition Temperature of ponents were in good agreement with the experimentally de-
1800" F. for One Hour termined values.
Deviation, 5
Weight Added, Weight of .4sh, Based upon Size of Sample. Many samples submitted for ash analyses
Gram - Gram Based upon S-aCl have an ash content of 0.0017, or less, and for samples of so low
NaCl Fez02 Calcd.a Found total ash content
an ash content it is especially important to consider the influence
Unsulfate 0.0179 0.1225 0.1225b 0.1230 +O. 4 +2.8
0.0944 0,1229 0.1229b 0.1276 t3.6 +5.6 of the accuracy of the weight measurements upon the over-all
0.1727 0.1025 0.1025'~ 0.1092 i6.1 +3.9
0.2704 0.1027 0.1027* 0.1115 +8.5 +3.5 accuracy of the method. Khen an ordinary macrobalance is
0.2218 0.0783 0.0753b 0.0863 i-12.6 +5.0 used under routine conditions, an uncertainty of 0.2 mg. may be
0.0852 0.1062 0,10626 0.1122 +5.6 +7.0
0.0454 0.2070 0.2070; 0.2106 +1.7 +8.0 expected in each weighing. As two weighings are usually made in
Sulfated 0.0 0.1103 0.1103 0.1124 +1.9 . .. an ash determination, it is probable that a total of 0.3 mg. will be
0.0956 0.1028 O.218gc 0.2163 -1.2 -2.2
0.0850 0.1062 0.2094c 0.2086 -0.4 -0.1 experienced in the over-all operation (the major portion of this
0.1838 0.1040 0.291OC 0.2933 +O. 8 i1.2
0.1857 0.1004 0,3263C 0.3191 -2.2 -3.2 error is due to the fact that the weight of a large dish can vary as
0.0108 0.1096 0.1227c 0.1231 +3.2 i3.1 much as 0.1 to 0.2 mg. because of changes in pressure, tempera-
a Ash content of oil (0.0010%) not included in calculation, since weight of
ash obtained from 50-cc. portions used would be negligible. ture, and humidity, 11). Assuming that an over-all accuracy
* Complete volatilization of iYaC1 assumed.
Calculated as iYa?SO4 plus FetOs. of a t least 10% on the ash determination is desired, it follorvs that
the ash obtained from the burning operation must weigh a t least
as much as 3.0 mg. For instance, if the ash content of a sample
the dish. This may be caused by too rapid a rate of combustion is 0.001%, at least 300 grams of sample must be burned.
and/or by surface turbulence which may cause a spray of oil
droplets to ignite above the surface of the oil. Traces of water
are known to cause this turbulence, as do oils containing a mix- Table VI. Accutacy of Alodified Ashing >lethod on
Synthetic Samples
ture of hydrocarbons of mixed boiling ranges. By carefully A. Results Obtained by Ashing Oil Containing Known Weights of
controlled combustion these losses can be minimized, To deter- Solid Feros and IVaCl
mine the degree of mechanical entrainment of an ash in the smoke Weight b d d e d , Gram Total Ash, Veight %
NaCl Fez03 Calculated By analysis Deviation, %
during the burning operation, a number of experiments have been
0.0 0.0399 0.0798 0.0806 4-1.0
performed with both synthetic mixtures and regular plant samples. 0.0 0.2394 0.4788 0.4754 -0.7
I n general, the data obtained from these experiments, while not 0.0402 0.0 0.0804 0.0806 t0.3
0.0792 0.0 0.1584 0.1566 -1.1
entirely conclusive, have indicated that under careful combustion 0.0470 0.0386 0.1712 0.1722 +0.6
0.1396 0.0142 0,3076 0,3044 -1.0
conditions the systematic error introduced as a result of mechani- 0,0127 0.1563 0.3380 0.3408 iO.8
cal entrainment probably does not exceed about 5 to 8% of the Samples prepared by adding indicated quantities of NaCl and/or Fez08 to
ash from those samples. The results cannot be said t o be entirely 50-gram samples of oil having a determined ash content of 0.0068 weight
70. All synthetic compositions corrected for ash content of base stock.
conclusive because the synthetic samples used in these studies B. Results Obtained Using Or anometallic Compounds Dissolved i n
may or may not simulate the normally occurring metallic constit- G h i t e Oil
uents in the petroleum oils. The evidence upon which these Total Ash, Average
Weight % Found,
conclusions are based is discussed briefly below. B 3' By Weight
synthesis analysis % % Error
A plant sample was burned by the normal combustion proce- Na naphrhenate in white oil 0.0011 0 , 0 0 0 9 0.0009 -18.2
dure for a prolonged period and the smoke formed in the burning 0.0009
operation was collected on a cool surface. Analysis of this ma- Xa naphthenate in white oil 0.0100 0,0091 0.0092 -8.0
terial showed that it contained an amount of ash equivalent to 0.0092
about 6% of the ash content of the original sample. 0.0093
Saphthenates and oleates of Fe,
I n another experiment knoan weights of sodium as sodium S i , V, and Cr in white oil 0.0534 0.0531 0.0542 4-1.4
naphthenate were dissolved in highly refined white oil and 0.0547
burned. The coke portion of this sample was treated with con- 0.0549
Naphthenates and oleates of Fe,
centrated sulfuric acid (to convert the sodium to sodium sulfate S i , V, and Cr in white oil 0 0017 0.0019 0 00195 t14.5
and thus minimize loss of ash due to volatilization) and ignited to 0 0020
a constant weight. Results obtained from the experiments are
tabulated in Table \-I, Part B. The loss experienced during the
combustion operation amounted to about SC7, for a sample con-
taining 100 p.p.m. of sodium. The conclusions regarding size of sample necessary to obtain
A number of synthetic mixtures prepared either by adding solid the desired degree of accuracy in the ashing tests are based upon
sodium chloride and/or ferric oxide to oil, or by adding soluble the use of a conventional macrobalance having a normal uncer-
metallo-organic compounds of iron, nickel, chromium, and
vanadium to highly refined white oil, have been analyzed by the tainty of about 0.2 mg. under routine operating conditions.
modified ashing procedure developed during this investigation, For balances of greater precision, the above conclusions do not
with results as shown in table VI. There is no evidence of a sys- apply, as the size of the sample necessary t o obtain a suffrcient
tematic error in these determinations. quantity of ash for accurate weighing will be less than indicated
I n a series of experiments with synthetically prepared samples
made by using radioactive tracers of compounds of sodium, cal- above. B limited amount of work has been performed to ascer-
cium, and iron, Morgan and Turner (16) shoxed that if the type tain the feasibility of utilizing a microtechnique in the ash deter-
of additives used in this study adequately represented the addi- mination, so as to take advantage of the small sample require-
tions of a normally occurring metallic contaminant, the losses ments t o reduce the over-all time of analysis. I n Table VI11
attributable to entrainment and volatilization of ash components
are not of great significance in a properly conducted analysis. are shown the results obtained by the modified ash technique
Morgan and Turner defme carefully controlled conditions as being (described below in detail) and by the microtechnique on portions
a slow rate of combustion and the final ignition temperature not of the same sample. Except for sizes of sample and equipment
to exceed 550" C. (1022" F.). involved, the micromethod is essentially the same as the macro-
I n another experiment designed to determine the extent of
mechanical entrainment during burning, a series of blends of two method. The results obtained by the two methods on a sample
oils of widely diverging ash content was repared and each of of oil which contained approximately 20 p.p.m. of ash arecompara-
these was subsequently ashed. One oil h a f a n ash content of 1.6 ble, even though the size of the sample required by the micro-
p.p.m. and the other had an ash content of 74.5 p.p.m. The ash method is only about 10 grams as compared with about 1500
contents of the various blends were determined. It would be ex-
pected that if losses by mechanical entrainment were appreciable, grams required by the macromethod. Blank runs on platinum
the amount of the loss would increase as the ash content of the dishes (about 7 grams in weight) have indicated that the average
V O L U M E 24, N O . 11, N O V E M B E R 1 9 5 2 1737
to place the dish in the oven to remove the accumulated coke be-
Table VII. Effect of Ash Content on Losses by Mechanical fore burning additional portions. Subtract the weight of the dish
Entrainment from the weight of the dish plus contents after constant weights
have been obtained. The difference represents the weight of ash
Composition of Blend, ~~~~~t of in the sample.
wt. Blend -ksh Ash Content of
Heating Burned, Formed, B1end,P.P.l\l.
oil Petrolatum Grams Mg. Found Calcd. Accuracy and Reproducibility of Modified Ashing Procedure.
100 0 307 0.65 . ~
Because of the lack of information concerning the composition of
ashes in petroleum, it was not possible to prepare synthetic miu-
tures that were known to simulate such samples exactly in com-
position. However, the method was evaluated for accuracy
using tTTo types of synthetic samples: The first type was pre-
pared by adding known amounts of ferric oxide and/or sodium
Table VIII. Comparison of nlicro- and Macromethods for chloride to an oil of low and measured ash content, and the
Determining Total Ash
second type was prepared b;- adding knoll-n amounts of metallo-
Macro RIicro -
Size of sample, grams 1533 1646 9.49 9.79 organic compounds to a highly refined nhite oil. The results
Net weightof a s h , g r a m 0,0299 0.0326 0.000205 0.000208 obtained from the analyses of synthetic mixtures prepared in
Ash, 70 0,00195 0.00198 0.00216 0.00212
this manner are shonn in Table VI. For the first type of syn-
thetic mixture, an average error of about j=l%was obtained over
the concentration range of about 0.08 to 0.34 Tyeight % ash.
deviation from the mean experienced in a series of weighings
For samples of the second type, the percentage error ranged from
of these dishes amounts to about 0.026 mg. for a new dish and
about 18 t o 2% over the concentration range of 0.001 t o 0.05
0.030 mg. for a used dish. On a percentage basis, this error weight % ash.
is of about the same order as that experienced in the macro-
I n addition t o the limited data on synthetic mixtures, the modi-
method for the sample sizes required. In all probability this error
fied method has been further evaluated by a number of repro-
in the microprocedure could be reduced considerably by employing ducibility studies conducted on typical plant samples. Results
tared weights. As a microdetermination can be carried out with obtained from a number of multiple determinations on various
accuracy equivalent t o the macroprocedure, it is recommended
samples are shown in Table IX. The relative per cent standard
that whenever limited amounts of sample are available, this
deviation of individual stocks varied from 1 to 10% over the
procedure be employed.
concentration range of 0.02 to 0.25 Jveight %ash.
Modified Ashing Procedure. SAMPLING. The entire content
of the bottle in which the sample is submitted should be used for
the analysis, to minimize the effect of stratification. It is recom-
Table IX. Reproducibility Studies Using RIodified Method
mended that the quantity of sample submitted be governed by for Determining Total Ash
the approximate ash content according ta the following schedule: Arith- Standard
metical Deviation, s-
Approximate Ash Quantity t o Be Poured into Ash Content, Mean, ua nf".
W t . 7c
/"

Content, P.P.M. Clear Sample Bottle, Grams6 Sample W t . 70 Wt. % mean

2-10 1500-300 Gas oil 0.0197 0.0207 0.0203 0.0016 7.9
10-100 300-50 0.0214 0.0213
100 or more 50-20 0.0174 0.0216
a A clear bottle is preferred, SO that particles clinging to the walls of the Still bottoms 0.092 0.105 0.097 0 0046 4 7
container can be readily detected. No. 3 0.093 0.098
0.096 0.097
If a larger quantity of sample than specified is submitted, the Still bottoms 0.042 0.053 0.044 0 0046 10 4
analyst should obtain as representative a portion as possible by so. "0 0.041 0.045
0.041 0.044
placing the container in a large oven t o liquefy the contents Still hottoms 0.062 0.066 0.063 0 00?3 4 0
completely and to lower the viscosity, then thoroughly mixing No. 10 0.061 0.061
0.061 0.066
and pouring an appropriate amount into a sample bottle.
Still bottoms 0.073 0.074 0.069 0 0047 6.8
PROCEDURE. Weigh the sample bottle and transfer the con- h-0. 90 0.071 0.062
0.066 0.066
tents to a weighed platinum dish. (-4
porcelain dish may be sub-
stituted for a platinum dish in most cases where the sample upon Fuel oil 0.124 0.123 0.123 0.0014 1.1
No. 24 0.121 0.124
ignition does not stain or attack the glazed surface of the dish.
The ash can be weighed, after complete ignition, by transferring Fuel oil 0.170 0.170 0.171 0.0035 2.0
s o . 33 0.172 0.168
it quantitatively to a tared a a t c h glass.) The dish should never 0.174 0.177
be filled to more than tao-thirds of its capacity; hence it may be 0.167 0.169
necessary to conduct a burning operation in several steps. Rinse Fuel oil 0.250 0,238 0.253 0.0109 4.3
out the last traces of sample from the bottle with xylene, taking No. 25 0.255 0.262
care to remove all particles clinging to the walls. A4ddthe xylene 0.268 0.246
washings to the dish along with the sample. Reweigh the dried Fuel oil 0.240 0.242 0.239 0.0090 3.8
sample bottle; the difference between this weight and that of the No, 15 0.264 0.23:
0.228 0.232
full bottle represents the weight of the sample. Cautiously apply
a flame of low intensity to the bottom of the dish until the con-
tents start to burn slowly. (If the sample contains appreciable
amounts of water, as indicated by sputtering when heating, place The accuracy of the modified ash determination was further
the dish overnight in an oven maintained a t 212" F.) When the demonstrated by an experiment in n-hich a portion of a sample of
sample begins to burn, remove the flame and allow the combus-
tion to proceed. If combustion ceases, reignite with the flame and filtered petrolatum was ashed by the modified ashing procedure
allow the burning to pfoceed until no liquid remains in the dish. and this result compared n-ith the results obtained by a n e t
Toward the end of the initial combustion place the dish on an oxidation of another portion of the same sample. The portion
electric hot plate so as to ensure complete burning of any tarry
material that may be present. I n some cases it may be necessary of the sample that was oxidized by concentrated sulfuric and
to apply a flame again to remove the tarry matter completely. nitric acids was analyzed for the individual metallic components,
When the combustion is complete, place the dish in a'muffle which summed u p to a total ash content of 60.6 p.p.m. This
oven maintained a t 1000° & 50" F. Continue ignition until suc- may be compared t o the ash content obtained by the modified
cessive weighings agree within 0.3 mg. Two to 7 hours may be ashing procedure of 58.7 p.p.m. which is an average obtained on
necessary for this operation, according to the amount and type of
carbonaceous material present. When a large amount of sample six determinations. The data for this experiment are shown
is used, it may be necessary after a portion of the sample is burned in Table X.
1738 ANALYTICAL CHEMISTRY
After the sample has been put into solution using the mixed
Table X. T o t a l Ash by W e t Oxidation acids, a n aliquot may be withdrawn for the sodium and potassium
determinations. The remaining portion is poured into a solution
P.P.M. in Oil of sodium hydroxide containing sodium peroxide, which precipi-
Elements Determined after (after Blank
Digestion in HzSO4 and HKOi Calculated as Subtraction) tates the iron, nickel, and titanium as the hydroxides, while the
Sodium vanadium and the chromium are converted to water-soluble
Silicon vanadates and chromates. It is necessary to redissolve the iron,
Iron nickel, and titanium hydrosides and then to reprecipitate them in
Sickel order to remove possible occlusions of chromium and vanadium.
Vanadium
Chromium The residue containing the hydroxides of nickel, titanium, and
__ iron is put' into solution by treatment xith acid; the nickel is
Total 60 6
isolated by adding sodium citrate, ammonium hydroxide, and
Total ash by modified ashing procedure 58 i o
dimethylglyoxime to precipitate nickelous dimethylglyoxime,
a Average of 6 determinations which is then extracted with chloroform. Iron and titanium are
determined on separate aliquots after the nickel has been re-
inoved. Chromium and vanadium, in the alkaline portion, are
separated by the reaction of vanadium with 8-quinolinol and ex-
traction with chloroform a t a definite pH.
COLORIMETRIC METHODS FOR DETERMINING An alternative procedure, which was used in t,his laboratory
INDIVIDUAL COMPONENTS until it was noticed that most of the ash samples went into s o h -
tion readily with hydrochloric and sulfuric acids, consists of
The determination of individual components in the ash is fusing the sample with eutectic mixture of sodium and potassium
different from the conventional analysis of minerals only in that carbonates plus a small amount of sodium nitrate. This fusion
mixture makes the vanadium and chromium wat'er-soluble, con-
the amount of sample available is usually euceedingly small and verting the iron, nickel, and titanium to insoluble oxides, which
the usual gravimetric or volumetric procedures are not sufficiently may be brought into solution by subsequent fusion with potas-
sensitive. Hence, colorimetric methods which are sufficiently sium pgrosulfate. The separation and determination of chro-
sensitive may be employed advantageously. Many colorimetric niium a.iid vanadium and of nickel, iron, and titanium are carried
aut as described above, after the initial separation is made with
methods allow satisfactory determinations t o be made when only tile sodium hydroxide-sodium peroxide solution.
a few hundredths of a milligram of the component is present.
Colorimetric techniques have been applied t o the determination ilfter the above steps, each element may be determined by
of iron, nickel, vanadium, titanium, and chromium; sodium and colorimetric methods ( I S , 19, 21, :?2) using specific reagents-for
potassium have been determined by flame photometry, which is
example, iron with ammonium thiocyanate or with o-phenanthro-
perhaps equally eensitive. Calriuni, silicon, and magnesium
line, nickel with dimethylglyoxime, chromium with diphenyl
have been determined by usual gravimetric determinations; how-
carbazide, titanium with hydrogen peroside, and vanadium with
ever, colorimetric or other procedures suitable for the deterniina-
tion of micro amounts are available for these elements and could either hydrogen peroxide or phosphotungstic acid. The concen-
perhaps be readily adapted to this service. trations are determined by measuring the respective color intensi-
In the determination of the constituents of an ash it is neces- ties with a photoelectric colorimeter or a spectrophotometer and
sary that the entire sample be put into solution and that a semi- comparing these readings n-ith previously prepared calibration
micro chemical separation be made in those cases where the pres- curves. The optimum concentration range, the absorbance of
ence of one element interferes with the accurate determination the color complexes, and a fern critical factors for several elements
of the otheIs Sodium and potassium can be determined rapidly are presented in Table S I . As these methods (13, 19, 21, 2 2 )
and satisfactorily on an aliquot portion of the solution by using the have been adequately reported in the literature, no further de-
flame photometer, provided the analyst is cognizant of possihle scription of details are presented here.
mutual interferences of the
elements listed ( 2 ) .
The ash may be put into
solution by fusion n ith potas- Table XI. S u m m a r y of Colorimetric Procedures
sium pyrosulfate or sodium car-
bonate-sodium nitrate, or by
treatment with hydrochloric
and sulfuric acids. While theie Iron Thiocyanate (19,p. 363) 0.2 to 5 0 540 Time of standing kind of
has been no attempt t o stand- (21, p. 307) acid, concentration of SCK,
( f 3 ,p. 409) light, presence of other
ardize upon either method of ( 2 2 . pp 218, 237) anions
putting the sample into solu- o-Phenanthroline 119, p. 375) 0 4 to 8 0 500 Acid range, p H 2-9, color
(81, p. 314) very stable, interference of
tion, the acid treatment is pre- (IS, p. 318) other ions can be corrected
ferred when it can be used a5 Nickel Dimethylglyoxime (19,p. 470) 0.1 t o l . 5 325 Color stable 1 5 minutes; hue
it does not introduce into the (21, p. 345) of color depends on acidity;
( I S , p. 502) 0.25-0.50 N HC1 produces
sample a large amount of alka- no change
line salts which prevent alka- Yanrtdium Hydrogen peroxide (19, p. 609) 3 to 60 470 Acid not critical b u t peroxide
( S f ,p. 453) concentrations should be in-
line metal analyses from being creased as acid increases.
carried out. Stable 24 hours, fading due
t o loss of peroxide
In most of the cases of ashes Phosphotungstate ( 1 9 , p. 607) 0.5 t o l l 400 S o t applicable in presence of
analyzed in this laboratory, (21, p. 45.5) large amounts of K. Mole
ratio of phosphoric acid t o
solution was readily effected sodium tungstate lies in
by use of hydrochloric and rangeof 3:l t o 2 0 : l
sulfuric acids. Any silica in Titanium Hydrogen peroxide (19, p. 572) 3 TO 30 420 Alkaline sulfate causes bleach-
the sample (appearing as an in- ( 2 1 , p. 431) ing which can be compen-
soluble residue after the acid ( 2 2 , p. 384) sated by increased acidity.
Peroxide should be in-
treatment) is separated and creased as acidity increased
decomposed with hydrofluoric Chromium Diphenylcarbazide (19, p. 260) 0 02 t o 0 8 540 Although acidity is not criti-
acid. Following the treatment (81, p. 274) cal 0.2 ,\' is optimum; Fe
with sulfuric acid to remove (IS, p. 316) and large amounts of V
fluorides, all soluble portions (22,p. 167) interfere
are combined.
V O L U M E 2 4 , N O . 11, N O V E M B E R 1 9 5 2 1739

ter of the discharge and in consequence its uniformity during

Table XII. Identification of Geological Source of excitation (6). Thus the excitation is uniquely different from
Crude Oils" that of metal or inorganic spectroscopy. The high sensitivity
_ Chemical,
__~ P.P.1zI.
__ required for direct inspection may require techniques which are
Geological Spectroscopich, P.P.11. Ash
l'orniation Sa Fe A1 V Xi residue Sa Fe susceptible to extraneous traces that interfere in measuring the
Devonian 1.1 0.4 0 7 3.1 3.6 26 3.0 0.3 sought elements. Moreover, as is often the case with methods
Silurian 1 4 0.4 < 0 . 2 0 6 0.9 41 1.1 3.1 possessing high sensitivity, relative precision must be sacrificed
Ellenburger 0 . 7 0.3 < O 2 <0.2 1 7 16 0.6 1.6
0 Analyses performed o n 2 0 R bottoms concentrate by diptillation ani!
to achieve the speed and unequivocal identification which spectro-
results calculated o n crude charge stock. scopic techniques afford. Many problems are encountered
b Silicon was chief elemental component.
in the petroleum industry, however, v-here a measure of relative
precision can be sacrificed and yet the essential information
Table XIII. Charge to Electrical Desalting Treatment in
Spectroscopic Trace Metal Analysis of Crude Oils needed by direct spectroscopic inspect ion on an oil can be acquired.
Sample Kumber
The following are samples of such applications in which the
I z 5 cathode layer technique is employed in the direct inspection of
Desalting Performance oils.
Trace N e t a l Satisfactory Satisfactory Unsatiyfartory
P.p.m.
The results sho-m in Table XI1 were obtained in connection
nith studies on identification of geological origin of three crude
stocks. Both chemical and spectroscopic values were available
for sodium and iron; agreement between the two methods is fair.
Unique differences in properties or composition were sought,
IT hereby distinction as t o formation source might be made.
Although other physical and chemical tests were carried out on
these crudes, none gave definitive indexes as marked as differences
in trace elemental content, specifically of vanadium and nickel.
EMISSION SPECTROSCOPIC METHODS
In other instances of this type where sample amounts of the oils
Spectroscopic methods have cert,ain unique advantages not were limited, the spectroscopic method has proved ibs utility,
possessed by other schemes of analysis. The problem imposed especially in providing results not obtainable by other available
by chemical manipulations and steps of separation, such as methods.
usually are required in colorimetric procedures, for example, The values for trace metal content of crudes to desalting are
are not inherent in spectroscopic techniques in which the unaltered shown in Table XIIII. Among other test results obtained, it
sample may be directly inspected. Simple admixture of the was found that the stock exhibiting unsatisfactory desalting per-
sample with a standard substance often is the only prerequisite formance also contained a higher content of trace metals.
to an analysis from the emission spectrum. The spectroscopic
method is specific and essentially free of interference, it is rapid,
and it provides adequate sensitivit,y for determining most or Table XIV. Analysis of Saphthas for Trace Copper
all the commonly occurring trace metals in petroleum and its Contamination
fractions. bample Copper Content, P.P.M.
Spectroscopic applications described in the literature may be Designation Syntliesie Cheniicala Spectro-copic
essentially classified as direct or indirect, depending on the pro- S ~ n t h e t i cS o
1 1.2 : 3 1. I
cedure or preliminary treatment of the sample required prior to 2 2.5 3 4
anal?-sis. By the direct method the trace metals are excited as
such in the oil; by the indirect method the analysis is performed *
3

(i
7.8
11.7
28.3
117
10.9

I 1 ,j
7.6
13.2
22.5
103
on a distillation residue, char, ash, or other suitable concentrate
in which the trace metals have been segregated from most or I'lant S o .
all of the original oil sample.
Direct Spectroscopic Methods. Direct methods which have
been applied to oils differ chiefly in the manner in which the
sample is introduced into the arc, spark, or flame for excitation.
Calkins and White (3) impregnatcd hot carbon electrodes by Dithiocarbamate colorimetric iiietlioil o n a?h residue.
quenching them in the oi!, sothat the sample might subsequently
be subjected to a high voltage spark for determining additive Table X\-. Determination of Sodium in Heating Oils by
elements in lubricating oils; no application of the method to Emission Spectrum
naturally occurring trace metals n-as reported. Carlson and - \-a, P,P.11.
~~ ~-
Gunn ( 4 ) have employed an electrode impregnation technique, Eniission Flame"
Sainple spectrograph photorneter
however, in which the highly sensitive carbon arc cathode layer
9 8 5
is utilized in the direct inspection of petroleum-containing non- 25 19
52 52
additive metals in concentration ranges of 2 to 100 p.p,m. Other 4 i8 63
methods of introducing an oil into the arc or spark include the a Analysis made o n dilute arjiirous HC1 extract of oil.
porous cup ( 8 ) and the rotating electrode ( 1 7 ) techniques for
emission spcctrographic analysis, and the spray atomizer tech-
nique (6) for flame photometric analysis. Although these
latter devices and trchniques probably have potential use for The results of direct spectroscopic analysis on naphthas con-
the direct determination of naturally occurring trace metals, thus taminated with copper are shown in Table XIV, including the
far they reportedly have been applied only to the determination results obtained by chemical analysis on the same samples.
of additive elements. -4greement between the methods is fair, which indicates that thc
All direct methods employing the spectrographic arc or spark direct spectroscopic method is satisfactory for this test.
on oils have a common disadvantage in that the composition of Both emission spectrograph and flame photometer results for
the discharge z o n e b e i n g essentially that of the nonconductive sodium content of heating oils are presented in Table XV t o
oil during part or all of the discharge period-influences the charac- demonstrate the order of agreement observed between these
1740
rapid methods in control testing. More recent developments in
flame photometry are being employed, which enables the inspec-
tion to be made directly on the oil by injecting it into the flame,
thus resulting in additional advantages for the short-cut methods.
Indirect Spectroscopic Methods. The combustion of an oil is
the most commonly used procedure for concentrating trace
metals in the indirect method of spectroscopic analysis. The
concentration serves the dual pulpose of increasing manyfold the
emission intensity of the sought elemacts and of converting the
mineral matter into a form more amenable to control in analysis.
The ash residue resulting from ignition may be admixed in known
ratio with a suitable substance to produce a standard matrix
in which the excitation characteristics are comparatively well
controlled and reproducible. Various basic materials are em-
ployed in preparing a standard matrix, the choice of the material
selected being somewhat dependent upon such considerations
as the excitation energy level required, spectral measurement
interference, and convenience in preparation. Murray and Plagge
(16) used high purity silica as an “ash aid” and, following combus-
tion, added spectroscopic carbon preparatory to the spectro-
scopic analysis. Bnderson and Hughes ( 1 ) also employed a
silica matrix in determination of vanadium in bunker fuel ash,
using titanium as the internal standard. Hansen et al. employed a
special cup electrode as the combustion receptacle in which a few
drops of Diesel lubricant are burnt prior t o the spectroscopic
analysis (IO). This laboratory employs lithium carbonate as
the basic ingredient of a matrix on which milligram quantities
of ash residue from catalytic cracking feed stock oils are deter-
mined. Besides the considerable savings in time realized in the
analysis of ash matter from such stocks, the spectroscopic method
also is capable of providing a sensitivity and precision for all
the metals which is comparable with, or superior to, that pro-
vided by other available methods.
Table XVI. Typical Feed Stock to Catalytic Cracking in
Spectroscopic Analysis of Ash Residue
(Oil sample, 850 grams. Ash residue, 0.0052 gram)
Content
Element On ash, 7% On oil, p.p.m.
v 1.4 0.09
Si 4.1 0.25
Fe 16.5 1.01
Si 2.9 0.18
Na 8.5 0.52
Ca 8.5 0.52
Mg 1.5 0.09
41 < 1.0 <0.06
Cr < 1.2 <0.07
To illustrate application of the standard matrix technique in
the analysis of catalytic feed stock ash matter, typical results are
presented in Table XS’I. The time requirement for obtaining
the elements on the minute ash residue is 2.5 hours. The tech-
nique is simple in that it does not require the manipulations of
separation and measurement employed in chemical procedures,
hence a large number of samples of this type can be analyzed
routinely at a nominal cost. Details of the experimental tech-
nique have been described (9).
In Table XVII are shown the results obtained by this labora-
tory in the determination of trace vanadium in crude and gas
oil samples which have been analyzed cooperatively by several
laboratories. The lithium carbonate standard matrix spectro-
scopic technique n-as utilized in obtaining the results shown.
Although vanadium was detectable in the mixed sweet crude ash,
the concentration was below the calibration range normally
employed in the analysis of ash residues The agreement be-
tween chemical colorimetric and spectroscopic results on the gas
oil, in which the vanadium concentration of the ash is greater,
is satisfactory.
The true accuracy of both the emission spectrographic proce-
dure and the ashing procedure (and the subsequent chemical
ANALYTICAL CHEMISTRY
analyses) cannot be ascertained, because lack of information
regarding the chemical composition of the petroleum renders it
impossible to prepare a synthetic sample of known composition
simulating plant samples. However, if it can be assumed that
the metals are present as oil-soluble organometallic compounds
such as ferric acetate, or nickel naphthenate, then some measure
of the accuracy can be obtained In Table XVIII the data are
reported for four synthetically prepared samples, Fhich may be
regarded as typical of results obtained as Tell as serving as a
cross check between the two methods Generally, an accuracy
of about f 1 0 to 4 ~ 3 0 %can be achieved by the emission spectro-
graphic method for determining iron, nickel, chromium, vanadium,
and sodium (in the presence of each other) over the concentration
ranges of 3 t o 100 p p.m. for iron and sodium and about 1 to 20
p.p.m. for the other metals. For the same type of sample colori-
metric determinations subsequent to the modified ashing tech-
niques achieve an accuracy nithin about & 8%.
SUMMARY
Minerals occur in petroleum products in amounts ranging from
a few parts per million to several tenths of a per cent, depending
upon the source of the crude and the history of the specific.
sample. There is evidence that these metallic constituents may
be present as an oil-soluble metallo-organic compound, a? a
colloid, as a filterable suspension, or as coarse particles dlthough
in certain cases the presence of metals in oils is deleterious to the
quality of the finished petroleum product, in other cases the pre+
ence of a controlled amount of specific oil soluble metals, such as
specially developed additives, bestows beneficial characteristics
on the finished product.
In order to correlate the influence of individual components
upon the product quality and to achieve plant control, it is
necessary to have available reliable analytical methods for deter-
mining individual elements as well as total mineral constituents.
The ashing of petroleum samples (comprising ignition of the oil
follo~vedby muffling to remove carbon) has long been employed
by the petroleum industry as a “shot gun” method to obtain
the total mineral constituents and to provide an ash for subse-
quent elemental analysis. An investigation of some of the steps
involved in the ashing procedure has ievealed that unless care is
exercised, this method may lead to erroneously low results.
There may be erratic results inherently due to the stratification
of a sample in its container. There may be losses due t o volatil-
ity of certain materials such as alkali, lead, and zinc halides or
vanadyl and chromyl-type compounds; and there may be losses
due to mechanical entrainment caused by too rapid burning or
the presence of moisture in the sample, nhich causes surface
turbulence.
Concurrently with the development and evaluation of the ash-
ing procedure, emission spectrographic procedures have been
developed (1) for the direct determination of various metals in
the oils by means of the cathode layer technique employing cobalt
and lithium as internal standards, and (2) for the analysis of
ash residues employing lithium carbonate as a common matrix
substance. While the determinations described represent some
progress in the field, additional analytical research and develop-
ment are still necessary. For example, the exact nature of the
mineral constituents should be further elucidated; the study of
the mechanics of burning and the volatilization characteristics
of any material that could be present should be continued; the
Table XVII. Determination of Vanadium in Oils from
Analysis of Ash Residues
Ash Content Vanadium on 4sh, %
on Oil, 7% Colorimetric Spectroscopic
Mixed sweet crude 0 0186 0 08 < 1 la
Process gas oil 0 00067 2 4 2 3
a Lower calibration limit.
V O L U M E 24, N O . 1 1 , N O V E M B E R 1 9 5 2 1741
(2) Broderick, E. J., and Zack,
Table XVIII. Total Ash and Metallic Constituents of Synthetic Oil Mixtures P. G., ANAL. CHEM., 23,
1455 (1951).
Sample 1 Sample 2 Sample 3 Sample 4 (3) Calkins, L. E., and White,
Syn- Syn- Emission Syn- Emission Syn- Emission XI. &I., Natl. Petroleum
Components thesis Chem. thesis Chem. spectrograph thesis spectrograph thesis spectrograph Sews, 38, No. 27, 519
Parts per Million (1946).
Total ash 534 531 17 19 .. .. .. .. .. (4) Carlson, AI. T., and Gum,
547 ... 20 ..
.. .. .. .. .. .. E. L., ANAL. CHEM., 22,
549 . I . ... .. .. .. 1118 (1950).
Fe 228 228 4.3 4.1 3 25 22 51 52
223 ... 4.2 4 .. 28 .. 42 (5) Clark, R. O., et al., Ibid., 2 3 ,
222 ... ... .. .. .. .. 1348 (1951).
Si 20 18.1 2.8 2.7 2.0 9 9 17 19 (6) Conrad, -4.L., and Johnson,
18.0
17.7 .. .. .. 2.7
... 1.0
.. .. .. 10 ., .. 17 IT. D., Ibid., 2 2 , 1530
V 8.1 8.2 1.5 1.6 1 3 ‘3 6 J (1950).
8.4 ... 1.5 1 .. 4 .. 6 ( 7 ) Evans, C. T., Bm. SOC.Test-
8.0 ... ... .. .. .. .. ..
Cr ... ... 0.37 0.34 0 6 8 11 14 ing Materials, Spec. Tech.
... ... ... 0.37 .. .. .. .. Pub., 108 (1950).
Na ,.. ... ... ... .. 14 16 2i 11 (8) Gassman, A. G., and O’Seill,
... ... ... ... , . .. 20 .. 22
W. R., ANAL. C H E M . , 21,
417 (1949).
(9) Gunn, E. L., and Powers, J.
hI., Ibid., 2 4 , 742 (1952).
colorimetric methods of analysis should be improved in sensitivity Hansen, J., Skiba, P., and Hodgkins, C. R., Ibid., 23, 1362
(1951).
and should be extended t o embrace other commonly occurring \ - - - - , .

Hillebrand, W,F., and Lundell, G. E. F., ”ilpplied Inorganic

materials including anions and the emission spectrographic pro-
cedures should be improved in accuracy and reproducibility and
extended in their applications.
I n view of the much loaer time requirements of the emission
spectrograph and the elimination of the bothersome problems
of entrainment and volatilization losses, it is felt that the direct
emission spectrographic technique offers a promising route t o the
final solution of this problem.
ACKNOWLEDGMENT
The authors a i s h t o acknowledge the aid and suggestions of
W. D. Seyfried and J. 11.Powers in preparing this paper, the
work of .4.E. Walters. M. T. Waddell, H. P. Hartley, and C. C.
Cochrane in ashing and chemical development and of Edra Joy
Hansen, Virginia Harleston, and Eugenia Smith in spectrographic
analysis, and t o thank the Humble Oil and Refining Co for per-
mission to publish the paper.
LITERATURE CITED
(1) Anderson, J. W,,
and Hughes, H K., Am. Petroleum Inst. Sym-
posium, 16th Midyear Meeting, 1951.
rlnalysis,” p. 14, New York, John \\?ley & Sons, 1929.
Lykken, L., Fitssimmons, K. R., Tibbetts, S. A., and Wyld, G.,
Petroleum Refiner, 24, No. 10, 405 (1945).
Mellan, Ibert, “Organic Reagents in Inorganic Analysis,”
Philadelphia, Blakiston Co., 1941.
Mills, G. A., Ind. Eng. Chenz., 4 2 , 182 (1950).
Morgan, L. O., and Turner, S. E., AX.AL.C H E M . , 23, 978 (1951).
Murray, X. J., and Plagge, H. h.,Proc. Am. Petroleum Inst.,
2 9 M , (III), 84 (1949).
Pagliassotti, J. P., and Porsche, F. W.,
-4x.4~.C H E M . , 23, 198
(1951).
Ritterhausen, E. P., and DeGray, R. J., IND. EXG.CHEM.,
AN.4L. ED., 14, 806 (1942).
Sandell, E. B., “Colorimetric Determination of Traces of
Metals,” 2nd ed., New Tork, Interscience Publishers, 1950.
Skinner, D. A, Abstracts of Papers, 119th Meeting of AMERICAN
CHEMICAL SOCIETY, p. 4-0, 1951.
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RECEITED
for review April 14, 1952. Accepted July 3, 1952.

Identification of Cyclohexanethiol in Virgin Naphtha

ROBERT C. ARNOLD, PHILIP J. LAUNER, AND ARTHUR P. LIEN
Research Department, Standard Oil Co. (Indiana), Whiting, Znd.

S ULFUR compounds in petroleum have an adverse effect on

the quality of petroleum products. Thiols are particularly
detrimental because of their disagreeable odor, strong corrosive
of fractional distillation, chromatography, infrared spectroscopy,
and the preparation of derivatives were employed in this study.

tendencies, and deleterious effect on product stability. EXPERIMEVTAL

The need for fundamental information on the nature of sulfur
compounds in petroleum has been recognized since the early days
of the industry (6). Increasing use of high-sulfur crude oils has
magnified this need and has resulted in the formation bythe Ameri-
can Petroleum Institute of Project 48, vhich has as one of its
objectives the separation and identification of sulfur compounds
in petroleum (7). Thiol, disulfide, sulfide, and thiophenic sulfur
compounds have been identified thus far. Aliphatic, aromatic,
and naphthenic sulfur compounds are theoretically possible, but
previous studies have led t o the positive identification of only
aliphatic thiols (S,7 ) .
The present investigation of the structure of petroleum thiols
has demonstrated the presence of relatively large amounts of
naphthenic thiols in high-sulfur virgin naphthas. The techniques
The sequence of operation follolved in the investigation was:
concentration of thiols by caustic extraction of the naphtha;
purification of the thiol concentrate by a combination of chemical
and physical means; separation of the thiols into narrow frac-
tions by distillation, followed by chromatographic adsorption;
and identification of individual sulfur compounds by preparation
of derivatives and by infrared spectroscopy.
Equipment. Thiol fractionation was conducted on a 4-fOOt X
1-inch glass column packed with ‘/*-inch single-turn glass helices.
The column, which had a rated efficiency of 35 theoretical plates,
was surrounded by a heating jacket so designed that heat input
could be varied over the length of the column and balanced
against heat loss. A differential thermocouple arrangement, in-
volving spaced pairs of thermocouples located in the dead-air