Naphthenic Acids in Crude Oils Characterized by Mass

Spectrometry
Chang S. Hsu,*
,
G. J. Dechert,

W. K. Robbi ns,

and E. K. Fukuda

Exxon Research & Engineering Co., Annandale, New J ersey 08801, and Rutgers University,
New Brunswick, New J ersey 08901
Received August 9, 1999. Revised Manuscript Received October 17, 1999
The presence of naphtheni c aci ds i n crude oi l s i s of concern i n the petrol eum i ndustry due to
thei r corrosi vi ty to refi nery uni ts. I t i s desi rabl e to determi ne the ri ng type and carbon number
di stri buti ons because the corrosi vi ty of naphtheni c aci ds i s dependent on the si zes and structures.
The characteri zati on of naphtheni c aci ds i s al so of i nterest to geochemi cal studi es, parti cul arl y
mi grati on and bi odegradati on, and to refi nery wastewater treatment for envi ronmental compl i -
ance. We have eval uated chemi cal i oni zati on, l i qui d secondary i on mass spectrometry (fast i on
bombardment), atmospheri c pressure chemi cal i oni zati on (APCI ), and el ectrospray i oni zati on i n
both posi ti ve and negati ve i on modes for the determi nati on of mol ecul ar di stri buti on of aci ds
wi thout deri vati zati on. Negati ve-i on APCI usi ng acetoni tri l e as a mobi l e phase yi el ds the cl eanest
spectra wi th good sensi ti vi ty among the i oni zati on techni ques eval uated. The sel ecti vi ty of
negati ve-i on APCI for naphtheni c aci ds has al so been demonstrated by compari ng resul ts for a
whol e crude oi l wi th those for the i sol ated aci d fracti on. APCI al so hol ds a great potenti al for
on-l i ne l i qui d chromatography-mass spectrometri c (LC/MS) to separate aci ds by hi gh-performance
l i qui d chromatography (HPLC) fol l owed by mass spectrometri c characteri zati on of aci ds.
Introduction
Naphtheni c aci ds, ori gi nal l y i denti fi ed as carboxyl i c
aci ds i n crude oi l s wi th si ngl e or mul ti pl e saturated
ri ngs, i s the phrase l oosel y used to i ncl ude al l aci di c
components i n crude oi l s that may even contai n aro-
mati c functi onal i ty. Thei r presence i n crude oi l s i s of
concern due to thei r corrosi vi ty to refi nery uni ts.
1-3
I t
i s hi ghl y desi rabl e to determi ne the ri ng-type di stri bu-
ti on and the carbon number di stri buti on of each ri ng
type because the corrosi vi ty of naphtheni c aci ds i s
dependent on the si zes and structures.
4
The character-
i zati on of naphtheni c aci ds i s al so of i nterest to geochem-
ical studies, particularly migration and biodegradation,
5-7
and to refi nery wastewater treatment for envi ronmental
compl i ance.
8
Mass spectrometry i s wel l sui ted for characteri zi ng
aci di c components at the mol ecul ar l evel . Due to thei r
pol ari ty, aci ds are commonl y deri vati zed to correspond-
i ng esters for detai l ed gas chromatography/mass spec-
trometri c (GC/MS) anal ysi s.
9,10
However, di rect aci d
anal ysi s i s more desi rabl e because i t can provi de rapi d
anal ysi s wi thout the concern of l osi ng materi al through
deri vati zati on. Several methods have previ ousl y been
devel oped for such purposes, i ncl udi ng fl uori de-i on
chemi cal i oni zati on
11
and negati ve-i on fast-atom bom-
bardment.
12
We have eval uated al ternati ve soft i oni za-
ti on techni ques, i ncl udi ng chemi cal i oni zati on (CI ),
l i qui d secondary-i on mass spectrometry (LSI MS), at-
mospheri c pressure chemi cal i oni zati on (APCI ), and
el ectrospray i oni zati on (ESI ), that woul d yi el d mol ecul ar
or pseudo-mol ecul ar i ons for the determi nati on of mo-
l ecul ar di stri buti on of naphtheni c aci ds.
Experimental Section
For CI experi ments a Fi nni gan TSQ-46B tandem quadru-
pol e mass spectrometer that was operated at a si ngl e-stage
mode was used. Onl y the most commonl y used reagent gases,
methane, i sobutane, and ammoni a, were used for the eval u-
ati on. I n i sobutane CI , for exampl e, an excess amount of
i sobutane was i ntroduced i nto a CI source unti l the forepump
pressure readi ng was at 0.4 Torr and the i on gauge readi ng
was 2 10
-5
Torr. At thi s pressure, i sobutane generates tert-
butyl i ons (57 Da) predomi nantl y to react wi th sampl e
mol ecul es. A smal l amount (l ess than 1 mg) of the sampl e was
deposi ted i nto a capi l l ary quartz tube that was then i nserted
* Correspondi ng author: Fax: (908) 730-3314. E-mai l : cshsu@
erenj.com.

Exxon Research & Engi neeri ng Co.

Rutgers Uni versi ty.

(1) Derungs, W. A. Corrosion 1956, 12, 617t-622t.
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J.; Ri chnow, H. H.; Mi chael i s, W. Org. Geochem. 1992, 18, 851-860.
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Moore, M. M. Environ. Toxicol. Chem. 1996, 15, 1482-1491.
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167, 149-158.
(10) Green, J. B.; Sti erwal t, B. K.; Thomson, J. S.; Treese, C. A. Anal.
Chem. 1985, 57, 2207-2211.
(11) Dzi di c, I .; Somervi l l e, A. C.; Rai a, J. C.; Hart, H. V. Anal. Chem.
1988, 60, 1318-1323.
(12) Fan, T.-P. Anal. Chem. 1991, 65, 371-375.
217 Energy & Fuels 2000, 14, 217-223
10.1021/ef9901746 CCC: $19.00 2000 Ameri can Chemi cal Soci ety
Publ i shed on Web 12/04/1999
Figure 1. Posi ti ve-i on i sobutane chemi cal i oni zati on mass spectrum of the TCI Aci d.
Figure 2. Negati ve-i on fast i odi de ani on bombardment mass spectrum of the TCI Aci d.
218 Energy & Fuels, Vol. 14, No. 1, 2000 Hsu et al.
i nto the cavi ty of a probe. The probe was then i nserted i nto
the i on source of the mass spectrometer through a vacuum
l ock. The sampl e was heated bal l i sti cal l y from ambi ent tem-
perature to 400 C vi a a heati ng coi l around the cavi ty of the
probe. I n the CI experi ments, both posi ti ve -i on and negati ve-
i on mass spectra of the sampl e were acqui red. A Fi nni gan
I NCOS data system was used for i nstrumental control and
data acqui si ti on.
For LSI MS experi ments a VG-ZAB reverse-geometry doubl e-
focusi ng mass spectrometer was used. A cesi um i odi de pel l et
i s heated to produce Cs
+
and I
-
i ons wi th an emi ssi on current
readi ng at 2 A. For naphtheni c aci ds the negati ve-i on mode
was found to be more effecti ve than the posi ti ve-i on mode. I n
the negati ve-i on mode, the sampl e was mi xed wi th tri ethano-
l ami ne (TEA) and bombarded by fast i odi de ani ons wi th a
ki neti c energy of 25 keV. The sampl e i ons generated from fast
i odi de ani on bombardment (FI AB) were extracted and accel er-
ated out of the i on source at 8 kV. A VG SI OS data system
was used for the i nstrument control and data acqui si ti on.
The APCI and ESI experi ments were carri ed out at Rutgers
Uni versi ty usi ng Mi cromass Pl atform I I mass spectrometer
(an i nstrument for l i qui d chromatography-mass spectrometry)
equi pped wi th a DECpc computer runni ng on a Versi on 2.2 of
the Massl ynxNTsoftware. The si ngl e quadrupol e i nstrument
can be operated i n ei ther the APCI or ESI mode. The sampl e
was di ssol ved i n acetoni tri l e and i ntroduced through a l oop
i njector onto the ti p of a heated APCI nebul i zer probe where
the mobi l e phase contai ni ng the sampl e was pneumati cal l y
converted i nto an aerosol and rapi dl y heated to 450 C i nto
vapor phase at the probe ti p. A corona di scharge pi n at 3 kV
was used to i oni ze the vapor from the nebul i zer. The source
temperature was mai ntai ned at 150 C. The sampl e and
reagent i ons passed through a counter el ectrode pri or to bei ng
expanded through a sampl e cone and ski mmer assembl y i nto
the mass spectrometer.
Mul ti pl e-scan carbon-13 nucl ear magneti c resonance (
13
C
NMR) spectra were acqui red wi th a Vari an Uni ty+ 500 MHz
NMR spectrometer. Sampl es are di l uted i n deuterated chl o-
roform (CDCl 3) to 30%sol uti on contai ni ng 25 mg of chromi um
acetoacetonate (CrAcAc) as a rel axati on agent per mi l l i l i ter
of the sol uti on.
The commerci al sampl es of naphtheni c aci ds for MS eval u-
ati on were purchased from Kodak, Fl uka, Pfal tz & Bauer
(P&B), and TCI Ameri ca. For the APCI sel ecti vi ty studi es,
naphtheni c aci ds were i sol ated from an aci di c Cal i forni an
crude oi l wi th TAN (total aci d number) of 4.06 mg KOH/g
sampl e by sol i d-phase extracti on wi th ami nopropyl si l i ca.
13
Results and Discussions
CI (l ow-pressure CI or conventi onal CI ) has evol ved
i nto a routi ne mass spectrometri c operati on.
14,15
Com-
monl y used reagent gases are methane, i sobutane, and
ammoni a, al though other gases can al so be used. For
(13) Morri son, B.; DeAngel i s, D.; Bonnette, L.; Wood, S. Pi ttCon/
92, New Orl eans, March, 1992.
(14) Harri son, A. G. Chemical I onization Mass Spectrometry, 2nd
ed.; CRC Press: Boca Raton, FL, 1992.
(15) Munson, B. Anal. Chem. 1977, 49, 772A-778A.
Figure 3. Negati ve-i on atmospheri c pressure chemi cal i oni zati on (APCI ) mass spectrum of the TCI Aci d.
Table 1. Conversion of Nominal z* Series to
Corresponding O2 z-Series
z* z (O2)
-10 0
-12 -2
-14 -4
-2 -6
-4 -8
-6 -10
-8 -12
Naphthenic Acids in CrudeOils Energy & Fuels, Vol. 14, No. 1, 2000 219
naphtheni c aci ds, the use of F
-
, Cl
-
, or OH
-
woul d be
expected to yi el d useful negati ve-i on CI (NI CI ) spectra,
but these reagent gases are not conveni entl y used
wi thout safety and operati onal concerns. I n our eval u-
ati on, both posi ti ve- and negati ve-i on modes were ap-
pl i ed usi ng common reagent gases i ndi vi dual l y. When
methane and i sobutane are used for NI CI , near-zero-
energy thermal el ectrons are generated, resul ti ng i n
resonance el ectron capture or di ssoci ati ve el ectron
capture. I n the case of al i cycl i c naphtheni c aci ds el ectron
capture i s not an effi ci ent process. I n addi ti on, el ectron
capture can be very effi ci ent for certai n pol ycycl i c
aromati c hydrocarbons that are not naphtheni c aci ds.
When ammoni a i s used for NI CI , very basi c NH
2
-
reactant i ons are generated. The NH
2
-
i ons can abstract
not onl y a proton from an aci d but al so a proton from
the benzyl i c posi ti on of aral kyl compounds. Thus, am-
moni a NI CI i s not sui tabl e for sel ecti ve i oni zati on of
naphtheni c aci ds i n crude oi l s ei ther.
I n the posi ti ve-i on mode, methane CI yi el ds excess
amounts of fragment i ons. Ammoni a CI yi el ds both
protonated and ammoni um-adduct mol ecul ar i ons wi th
overal l l ower sensi ti vi ty. The best CI spectra were
obtai ned wi th posi ti ve-i on CI usi ng i sobutane as a
reagent gas i n whi ch naphtheni c aci ds yi el d pri mari l y
protonated mol ecul ar i ons wi th mi ni mal fragmentati on.
FI AB i s a speci fi c type of mass spectrometri c tech-
ni que general l y known as LSI MS.
16-18
I n LSI MS, a
cesi um i odi de pel l et i s heated to produce Cs
+
and I
-
i ons. Dependi ng on the pol ari ty of the sampl e i ons to
be anal yzed, ei ther Cs
+
or I
-
i ons are accel erated by a
potenti al drop of 25 kV to bombard the target contai ni ng
the sampl e i n a l i qui d matri x. For the characteri zati on
of aci ds, the negati ve-i on mode was found to be more
effecti ve than the posi ti ve-i on mode because i t gave
cl eaner spectra wi th very good sensi ti vi ty. I n the nega-
ti ve-i on mode, the sampl e was mi xed wi th tri ethanol a-
mi ne (TEA) that i s used as a l i qui d matri x and bom-
barded by fast i odi de ani ons. Thi s woul d produce
deprotonated mol ecul ar ani ons of the sampl e by proton
transfer from the sampl e to TEA. Al though the sampl e
was bombarded by i odi de i on wi th hi gh ki neti c energi es
(25 keV), the i nternal energi es of the deprotonated
mol ecul ar ani ons are l ow, resul ti ng i n mi ni mal frag-
mentati on.
APCI and ESI are commonl y used i n l i qui d chroma-
tography/mass spectrometri c (LC/MS) experi ments.
19,20
We have found that ESI i s an order of magni tude l ess
sensi ti ve than APCI usi ng rel ati vel y nonpol ar sol vents
that are normal l y used for hydrocarbon mi xtures (unl ess
we anal yze water sampl es contai ni ng smal l amounts of
(16) Barber, M.; Bordol i , R. S.; El l i ott, G. J.; Sedgwi ck, R. D.; Tyl er,
A. N. Anal. Chem. 1982, 54, 645A-657A.
(17) Pachuta, S.; Cooks, R. G. Anal. Chem. 1987, 87, 647-669.
(18) Benni nghoven, A. I nt. J . Mass Spectrom. I on Phys. 1983, 46,
459-462.
(19) Brui ns, A. P. (a) MassSpectrom. Rev. 1991, 10, 53-78. (b) Trend
Anal. Chem. 1994, 13, 37-43.
(20) Garci a, D. M.; Huang, S. K.; Stansbury, W. F. J . Am. Soc. Mass
Spectrom. 1996, 7, 59-65.
Figure 4. Carbon number di stri buti on of i ndi vi dual ri ng type i n the TCI Aci d.
Figure 5. Typi cal naphtheni c aci ds.
220 Energy & Fuels, Vol. 14, No. 1, 2000 Hsu et al.
oi l s. I n that case, we can add a base to deprotonate the
aci ds for enhanced i oni zati on). For exampl e, usi ng
acetoni tri l e as a mobi l e phase the aci d wi l l be i n a
neutral form that woul d yi el d weak si gnal s i n ESI . I n
addi ti on, ESI i s more suscepti bl e to si gnal suppressi on
by matri x materi al s. I n APCI , the sampl e i s di ssol ved
i n a sol vent and i njected onto a l i qui d chromatograph
or a l oop i njector to transfer the sampl e mol ecul es to
the ti p of a heated nebul i zer. The mi xture of sol vent and
sampl e vapor i s then i oni zed by corona di scharge at 3-5
kV. For naphtheni c aci ds, acetoni tri l e has been found
to be a good sol vent and reagent gas. Acetoni tri l e i s
deprotonated to form the acetoni tri l e ani on, CH
2
CN
-
,
under the APCI condi ti ons. The aci d mol ecul es are then
i oni zed by proton transfer to CH
2
CN
-
, yi el di ng depro-
tonated mol ecul ar i ons wi th mi ni mum fragmentati on
and hi gh sensi ti vi ty.
Four commerci al sampl es of naphtheni c aci ds from
Kodak, Fl uka, Pfal tz & Bauer (P&B), and TCI were used
for the eval uati on. These aci d mi xtures represent aci ds
i sol ated from petrol eum fracti ons (typi cal l y gas oi l s)
from di fferent sources. Al though several MS techni ques
show si mi l ar resul ts for each aci d sampl e, the aci d
di stri buti ons among these commerci al sampl es di ffer.
21
The aci d sampl e from TCI (i .e., TCI Aci d) are used
bel ow to i l l ustrate the characteri sti cs of iC
4
-CI , FI AB,
and APCI . Fi gures 1-3 exhi bi t the posi ti ve-i on iC
4
-CI ,
negati ve-i on FI AB, and negati ve-i on APCI mass spectra,
respecti vel y, of the TCI Aci d. Note that posi ti ve-i on iC
4
-
CI yi el ds protonated mol ecul ar cati on, (M + H)
+
, whi l e
negati ve-i on FI AB and APCI yi el ds deprotonated mo-
l ecul ar ani on, (M - H)
-
. The mol ecul ar i on profi l es i n
the mass spectra are si mi l ar. However, iC
4
-CI gi ves
sl i ghtl y l ower carbon number di stri buti ons than FI AB
and APCI MS due to l ow vol ati l i ty of hi gher-mol ecul ar-
wei ght speci es. Si nce iC
4
-CI requi res vapori zati on of the
sampl e by di rect heati ng, decarboxyl ati on (thermal
decomposi ti on) of aci ds i s al so possi bl e. The l ow-mass
(21) Hsu, C. S.; Dechert, G. J.; Robbi ns, W. K.; Fukuda, E.; Roussi s,
S. G. Prepr. Pap.-Am. Chem. Soc., Div. Petrol. Chem. 1998, 43, 127-
130.
Figure 6.
13
C Nucl ear magneti c resonance spectrum of the TCI Aci d.
Figure 7. Ri ng-type di stri buti on of the TCI Aci d.
Naphthenic Acids in CrudeOils Energy & Fuels, Vol. 14, No. 1, 2000 221
i ons (<150 Da) observed i n iC
4
-CI are bel i eved to be
fragment i ons produced i n the chemi cal i oni zati on
processes. FI AB and APCI yi el d al most i denti cal mass
spectra. However, FI AB al so yi el ds aci d di mer cl usters
(>350 Da) due to i oni zati on i n a l i qui d matri x needed
for anal ysi s. Hence, APCI gi ves the cl eanest mass
Figure 8. Compari son of APCI mass spectra of the i sol ated aci di c fracti on (top trace) and the whol e Cal i forni an crude oi l from
whi ch the aci ds are i sol ated (bottom trace).
222 Energy & Fuels, Vol. 14, No. 1, 2000 Hsu et al.
spectra among the techni ques eval uated, i t does not
yi el d fragment and di mer cl uster i ons.
The mol ar masses of aci d components can be easi l y
obtai ned from the dal ton val ues of the protonated or
deprotonated mol ecul ar i ons. From the mol ar masses,
the ri ng-type di stri buti on of aci ds and the carbon
number di stri buti on i n each ri ng type can be deter-
mi ned. For exampl e, the deprotonated mol ecul ar i on of
237 Da shown i n Fi gure 3 corresponds to an aci di c
speci es of mol ar mass of 238. Usi ng the approach
suggested by Hsu et al ., the nomi nal mass seri es, z*, of
the 238 Da aci d can be determi ned to be -14 by the
remai nder of the nomi nal mass di vi ded by 14, i .e., the
modul us of (nomi nal mass/14) -14.
22
The nomi nal mass
seri es can then be converted i nto correspondi ng z-seri es
i n the general formul a of C
n
H
2n+z
O
2
for aci ds, accordi ng
to the Tabl e 1.
The 239 Da aci d i s i n the z ) -4(O
2
) seri es that i s
bel onged to 2-ri ng naphtheni c aci d (see bel ow). Once the
z-val ue i s determi ned, the carbon number of thi s speci fi c
aci di c speci es can be easi l y determi ned to be 15.
As for hydrocarbons, the di stri buti on of aci ds deter-
mi ned by mass spectrometri c anal ysi s can be conve-
ni entl y expressed by z-seri es where z represents hydro-
gen defi ci ency i n the mol ecul ar formul a of C
n
H
2n+z
O
2
.
For exampl e, acycl i c (0-ri ng) al i phati c aci ds have a
general formul a of C
n
H
2n
O
2
. The whol e seri es can be
expressed as z ) 0 (O
2
) seri es. One-ri ng naphtheni c
aci ds have a formul a of C
n
H
2n-2
O
2
. Hence, they can be
expressed as a z ) -2(O
2
) seri es. Fi gure 4 shows the
carbon number di stri buti on of seven aci d seri es i n the
TCI Aci d.
Fi gure 5 shows typi cal 1- to 4-ri ng naphtheni c aci ds
wi th z-val ues of -2 (O
2
) to -8 (O
2
), respecti vel y. Note
that 4-ri ng naphthenes share i denti cal mol ecul ar for-
mul a as benzenes. Hence, the z ) -8 (O
2
) seri es can be
ei ther 4-ri ng naphtheni c aci ds or an aci d seri es contai n-
i ng one phenyl group i n thei r hydrocarbon backbones.
Assumi ng that al l of the naphtheni c ri ngs are fi ve-
membered, the mi ni mum number of carbon atoms for
4-ri ng naphtheni c aci ds woul d be 14. However, the z )
-8 (O
2
) aci ds start at carbon number of 12 as shown i n
Fi gure 4. Thi s suggests that these are not 4-ri ng
naphtheni c aci ds, but rather aromati c aci ds wi th a
phenyl group i n the hydrocarbon backbones. Si mi l arl y,
the aci ds wi th z ) -10(O
2
) and -12(O
2
) start wi th
carbon numbers much l ess than the smal l est naphtheni c
aci ds wi th 5- and/or si x-membered ri ngs, suggesti ng
that they are aromati c aci ds as wel l . The presence of
aromati c aci ds i n the TCI Aci d was confi rmed by
13
C
NMR anal ysi s, shown i n Fi gure 7. The chemi cal shi fts
i n the 120-150 ppm regi on i ndi cate the presence of
aromati c carbons.
From the carbon number di stri buti ons shown i n
Fi gure 4, the carbonyl carbons are cal cul ated to be 6.8
mol % that agrees qui te wel l wi th 6.5% determi ned by
13
C NMR. However, the aromati c carbon esti mated by
MS i s 3.1%, compared to 5.4%determi ned by
13
C NMR.
The hi gher aromati c number by
13
C NMR i s probabl y
due to the presence of nonaci di c aromati c hydrocarbons
that are not detected by the sel ecti ve negati ve i on FI AB
and APCI techni ques. Fi gure 7 exhi bi ts the ri ng-type
di stri buti on of the TCI Aci d, whi ch shows that the most
abundant naphtheni c aci ds have two saturated ri ngs.
As di scussed above, the 4-, 5-, and 6-ri ng naphtheni c
aci ds are actual l y aci ds contai ni ng aromati c ri ngs. The
total amount of aromati c aci ds i s l ess than 10%.
To eval uate the sel ecti vi ty of APCI to the whol e range
of aci di c components i n a crude oi l , we have i sol ated an
aci d fracti on from a Cal i forni an crude oi l wi th hi gh aci d
content. The whol e crude oi l and i ts aci d fracti on were
separatel y i ntroduced i nto the LC/MS through a l oop
i njector wi thout chromatographi c separati ons. Fi gure
8 compares the negati ve-i on APCI spectrum of the
i sol ated aci d fracti on (top spectrum) wi th that of whol e
crude oi l (bottom spectrum). The si mi l ari ty of these two
spectra i ndi cates that onl y the aci di c components i n the
crude oi l s yi el d negati ve APCI i ons, l eavi ng other
components l argel y un-i oni zed. The TAN (total aci d
number, i .e., mg KOH/g oi l for neutral i zati on
23
) of the
crude oi l i s 4.06, whi ch i s equi val ent to 0.0725 mmol
aci d/g oi l . Wi th an average mol ar mass around 500
shown i n Fi gure 8 the aci ds woul d account for about
3.6% of the crude oi l by mass, consi stent wi th the
amount of aci ds actual l y i sol ated (3.9 mass %). Hence,
the sel ecti vi ty of the APCI techni que to the aci ds i n
crude oi l s i s demonstrated.
Conclusions
For the characteri zati on of naphtheni c aci ds, we found
that NI CI does not gi ve any advantages over posi ti ve-
i on CI , regardl ess of the reagent gas used (methane,
i sobutane, and ammoni a). I n addi ti on, the i nterferi ng
background i ons i n NI CI are di ffi cul t to el i mi nate. For
posi ti ve-i on CI , i sobutane was found to yi el d the cl eanest
spectra wi th good sensi ti vi ty over methane and am-
moni a. For FI AB and APCI , on the other hand, the
negati ve-i on mode was more sel ecti ve and sensi ti ve to
the aci ds than the posi ti ve-i on mode.
Negati ve-i on APCI usi ng acetoni tri l e as a sol vent and
mobi l e phase appears to yi el d the cl eanest spectra
among the mass spectrometri c techni ques eval uated for
the characteri zati on of aci ds, wi thout the di scri mi nati on
of heavi er i ons and the formati on of fragment and
cl uster i ons. APCI al so hol ds a great potenti al for
further devel opment of on-l i ne l i qui d chromatography-
mass spectrometri c (LC/MS) methods to separate aci ds
by hi gh-performance l i qui d chromatography fol l owed by
mass spectrometri c characteri zati on for the determi na-
ti on of aci d structures.
Acknowledgment. The authors acknowl edge the
13
C NMR spectrum of the TCI Aci d provi ded by Steve
Rucker and A. R. Garci a of Exxon Research & Engi -
neeri ng Co.
EF9901746
(22) Hsu, C. S.; Qi an, K.; Chen, Y. C. Anal. Chim. Acta 1992, 264,
79-89.
(23) 1998 Annual Book of ASTM Standards; Ameri can Soci ety for
Testi ng and Materi al s: West Conshohocken, PA.; Vol . 05.01, ASTM
D 664/I P 177.
Naphthenic Acids in CrudeOils Energy & Fuels, Vol. 14, No. 1, 2000 223