SPE 99884

Acid Number Measurements Revisited

T. Fan and J.S. Buckley, New Mexico Tech.

Copyright 2006, Society of Petroleum Engineers

This paper was prepared for presentation at the 2006 SPE/DOE Symposium on Improved Oil
Recovery held in Tulsa, Oklahoma, U.S.A., 2226 April 2006.
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Abstract
We propose an improved procedure for measuring acid
numbers and illustrate the significance of the results by
correlating with oil/brine interfacial properties.
Introduction
Chemical methods of improved oil recovery are not equally
effective in all reservoirs. An important factor that can
influence a project's success is crude oil composition. Since
crude oils are complex mixtures, evaluation of oil composition
in a way that is meaningful with respect to specific chemical
recovery processes can present many problems. In particular,
there is a need for improvements in acid number (AN), also
known as total acid number (TAN) measurements.
Acid numbers (AN) are important in evaluating crude oils
for alkaline and surfactant processes, but in order to be useful,
measurements must be comparable from one laboratory to
another and must also capture chemically meaningful
information about the crude oil. Standardization (e.g., the
current ASTM recommended procedure1) should assist with
the first requirement, that different labs be able to reproduce
the AN value within some reasonable tolerance.
Standardization does not, however, ensure that the
measurement captures information about a crude oil that can
be used to predict its interactions in chemical recovery
processes.
Acid number measurements attempt to characterize an oil
with respect to concentration of strong and weak acids by
means of non-aqueous potentiometric titration. The standard
procedure1 is designed to measure ANs in the range of 0.05 to
250 mg KOH/g oil. Stock tank samples of crude oil usually
have ANs that are at the low end of this range; strong acids are
not encountered. Thus the sensitivity of the ASTM method is
barely adequate for many samples of interest. According to
the ASTM procedure, 20 g of oil should be used if AN is less
than 1 mg KOH/g oil. Unfortunately, high quality samples of
crude oil are expensive to obtain and the quantity is very

limited. Using 20 g for AN measurement would often

preclude making any other measurements. The usefulness of
AN data is greatly increased if it forms part of a matrix of
information that includes, at a minimum, base number (BN),
SARA fraction data, and information about asphaltene
stability. There are few, if any, interfacial phenomena that
correlate exclusively to AN.
Basic constituents of an oil can also be assessed by nonaqueous potentiometric titration, but end-points are often more
difficult to detect because the organic bases that occur in crude
oils have a wide spread of dissociation constants. More than a
decade ago, Dubey and Doe2 published recommendations for
improved base number measurements by adding a known
amount of quinoline to force a readily detectible titration endpoint. Base numbers measured using spiked oil samples were
significantly higher than those measured by the ASTM
method and the higher base numbers were shown to correlate,
together with AN for the same oils, with observations of
wetting reversal on silica surfaces. A similar procedure was
shown to improve the precision of AN titrations using stearic
acid as the spiking agent for routine AN measurements.3
Precipitated material was observed for some crude oils in the
standard solvent (50% toluene, 49.5% isopropanol or IPA, and
0.5% water). Stearic acid and o-nitrophenol were used as
spiking agents by Zheng and Powers.4
No precipitation was reported in the base number solvent,
methyl isobutyl ketone (MIBK),3 which has been used as a
solvent for both acidic and basic titrations.4,5 Substitution of
tetrabutyl ammonium hydroxide (TBAOH) for KOH in the
titrating solution4,6 and MIBK for IPA as the titration solvent4
have been reported. A variety of electrodes have been tested
to overcome problems with slow electrode response times in
the non-aqueous environment.
In this work we have used stearic acid as a spiking agent
and varied solvents, titrants, and electrodes to optimize AN
measurement.
Experimental Materials and Methods
Crude oil samples. Acid numbers have been measured for
more than 250 crude oil samples. Table 1 summarizes
selected properties of the xx oil samples used as examples in
this paper. For each titration, a sample of 0.5 to 1.0 g of crude
oil was used.

SPE 99884

Table 1. Oil Properties

resins

(cP)
481
21.6
5.8

(wt%)
25.8
9.9
13.9

n-C6
asph
(wt%)
6.0
1.1
2.6

0
AN

BN

mg KOH/g oil
3.92
2.3o
0.22
1.23
0.17
0.62

Solutions.
Solvents. The solvent for most titrations was a mixture of
50% toluene (HPLC grade), 49.4% IPA (HPLC grade) and
0.06% deionized distilled water (DDW). MIBK was tested as
a possible alternative solvent with improved solubilization of
crude oil components.
A sample of crude oil was dissolved in 50 to 100 ml of the
solvent. More dilute solutions were prepared for heavy oils
whereas for light oils, more concentrated solutions were used.
Spiking solution. A solution was prepared of 0.02 M
stearic acid (Aldrich, 98+%) in the solvent described above.
Each AN measurement was spiked with 1 ml of this solution.
Titrant. Oil samples were titrated either with alcoholic
KOH (Aldrich, 99.99%) diluted to 0.05M in IPA or with
TBAOH (Aldrich, 1M solution in methanol) diluted to 0.05M
with ethanol. Titrants were calibrated with a solution of
potassium hydrogen phthalate (KHP) (Aldrich, ACS primary
standard) at a concentration of 0.002M in DDW.
Equipment. Two electrode systems were tested. The first
was an Orion 8101 glass pH electrode and an Orion 8005
reference electrode with saturated KCl in DDW as the
reference electrolyte. The second was an Orion 81-02
combination pH electrode with saturated Li Cl in ethanol as
the reference electrolyte. Comparable results were obtained
with both electrode systems.
A Brinkmann model 350 buret/dispenser was used to
deliver titrant at rates from 0.1 to 0.5 ml/min. Electrode
potentials (EMF in mV) were monitored with an Orion model
520 pH meter and were recorded by a computerized data
acquisition system.
Acid number calculation. Acid number can be calculated
from titration endpoints and equation (1).

AN =

(Vi Vb ) M MW

SQ-95
EMF (mV)

-200

-400

-600
0

0.5

1.5

volume of KOH titrant (ml)

Fig. 1. Potentiometric titration of SQ-95 crude oil shows no clear
inflection point.

Addition of stearic acid forces a sharp inflection point. In

Fig. 2, titrations of a spiked mixture with SQ-95 are compared
to a blank titration of the spiked mixture without crude oil.
The AN can be obtained from the difference between the
endpoints with and without crude oil. The value of the AN
thus obtained for SQ-95 is 0.2 mg KOH/g oil.
0
stearic acid in solvent + SQ-95

-100

stearic acid in solvent

-200

EMF (mV)

Mars-Pink
MY4-02
SQ-95

API
gravity
()
16.6
28.1
37.2

-300
-400
-500
-600

(1)

where
AN is acid number (mg KOH/g oil),
Vi is the volume of titrant at the sample inflection point (ml),
Vb is the volume of titrant at the blank inflection point (ml),
M is molar concentration of KOH titrant (mol/L),
MW is the molecular weight of KOH (56.1 g/mol), and
W is the amount of the oil sample (g).
Results and Discussion
Detecting the inflection point. If the ASTM method1 was
followed, only one of 40 titrations of different crude oil
samples had a clear inflection point. The titration of SQ-95
shown in Fig. 1 is typical.

0.2

0.4

0.6

0.8

volume of KOH titrant (ml)

Fig. 2. Potentiometric titration of SQ-95 crude oil spiked with
steric acid compared to a blank titration of stearic acid without
crude oil. Arrows mark approximate titration endpoints.

An alternative estimation technique is described in ASTM

D664 for samples without a clear inflection point.1 It involves
titrating standard solutions to determine fixed endpoints. The
alternative method gives a much higher value of 0.7 mg
KOH/g oil for this oil. Some further investigation of the
effects of adding stearic acid was undertaken to ensure that the
spiked solution results are not affected by specific interactions
between stearic acid and crude oil components.
Figure 3 shows tests in which a constant amount of stearic
acid was added to titrations of varying amounts of two quite

SPE 99884

different crude oils (see Table 1). The value of Vi varies

linearly with oil sample size for both SQ-95 (AN = 0.2 mg
KOH/g oil) and Mars-Pink (AN = 3.9 mg KOH/g oil). The
slopes are proportional to the AN of each oil and both linear
trends extrapolate to the value of Vb in the absence of oil.

200

EMF (mv)

volume of titrant Vi (ml)

SQ-95

KOH (aged 3 weeks)

Mars-Pink

KOH (freshly prepared)

100

-100
-200
-300
-400
-500

-600
0

0.2

0.4

0.6

0.8

volume of titrant (ml)

(a) titrant is KOH in IPA

200

0.5

1.5

2.5
100

weight of oil sample (g)

TBAOH (freshly prepared)

Blank titrations of the mixed solvent are difficult to

reproduce. When the blank is spiked with stearic acid,
however, the results are more consistent. Figure 4 shows, the
effect of solvent when a constant amount of stearic acid (0.022
mmol) is diluted to different concentrations. The titrant
reacted with stearic acid alone, obtained by extrapolation to
zero solvent, corresponds to 0.21 mmol. Thus spiking
improves the accuracy of both the crude oil and blank
endpoint determinations. The AN measured with spiked
samples is much more accurate than that estimated from
unspiked samples or from predetermined endpoints.
Titrants and solvents.
Comparison of KOH and TBAOH titrants. The ASTM
standard titrant, alcoholic KOH, must be freshly made and
standardized frequently. Figure 4a compares titrations of a
known amount of stearic acid by freshly made KOH titrant
and the same titrant three weeks later. The results with the
aged titrant are clearly unacceptable. If, however, the
alcoholic KOH is replaced by an alcoholic solution of
TBAOH, the titrant is much more stable. Results with the
freshly made and a three-month-old solution are comparable
(Fig. 4b).

EMF (mv)

0
Fig. 3. The volume of titrant varies linearly with the amount of oil
titrated. There is no evidence of specific interactions between
stearic acid and components of either Mars-Pink or SQ-95. (Note:
titrant is TBAOH in ethanol.)

-100

TBAOH (aged 3 months)

-200
-300
-400
-500
-600
0

0.2

0.4

0.6

0.8

volume of titrant (ml)

(b) titrant is TBAOH in ethanol
Fig. 4. Effect of titrant age on titrations of stearic acid. TBAOH in
ethanol is much more stable than KOH in IPA.

Acid numbers, measured in triplicate, are compared in

Table 2 for these two titrants. Values are the same, within the
accuracy of the measurements and standard deviations are
comparable. Where there is a difference, TBAOH is more
reproducible. Considering the improved stability shown by
solutions of TBAOH, we have adopted it as our standard
titrant.

SPE 99884

Table 2. Acid Number Measured with Different

Titrants
Mars-Pink
SQ-95

Titrant =KOH
AN (mg KOH/g oil)
3.92 0.05
0.17 0.02

1 - blank (before)

Ttitrant =TBAOH
AN (mg KOH/g oil)
3.95 0.02
0.22 0.02

3 - blank (after)

Alternative solvents. MIBK, the solvent used in base

number titrations, was tested as an alternative to the standard
mixture of toluene/IPA/DDW. As noted previously, no
precipitation was reported in MIBK solutions of crude oils.
Figure 5 shows the results of titrations for MY4-02 crude oil
solutions spiked with stearic acid in standard solvent and
MIBK. There is a clear endpoint in the standard solvent, but
not in MIBK. Other oil samples showed similar trends. Even
blank samples of stearic acid alone failed to produce clear
endpoints. We conclude that the standard solvent should not
be replaced by MIBK for AN measurements.

-200
-300
-400
-500
-600
0

0.2

0.4

0.6

0.8

volume of TBAOH titrant (ml)

0
MY4-02 in standard solvent mixture
-100

2 - SQ-95

-100

EMF (mV)

Crude oil

MY4-02 in MIBK

(a) A series of three measurements beginning with clean

electrodes: 1) a spiked blank solution, followed by 2) SQ95 crude oil, after which 3) a spiked blank solution was
remeasured.

EMF (mV)

-200

0
Run #1 - before

-300

Run #2 - before

-100

-400

Run #7 - after

EMV (mv)

-500
-600
-700
0

0.5

1.5

volume of TBAOH titrant (ml)

Fig. 5. Titration of MY4-02 crude oil, spiked with stearic acid, and
dissolved either in the standard mixture of toluene/IPA/DDW or in
MIBK. The standard solvent mixture produces much clearer
endpoints than does MIBK.

Electrode response.
Electrode responses change upon
contact with most of the crude oil samples that we have tested.
This is true for both two electrode and combination electrode
systems. Figure 6a illustrates this effect for the combination
electrode by comparing titrations of a blank solution spiked
with stearic acid, before and after contact with a spiked
solution of SQ-95 crude oil. Titration of the blank before
contact with crude oil produces a negative, physically
meaningless value for AN. Only if the blank is measured after
contact with the crude oil, so that the electrode response is
similarly affected for both measurements, can a realistic
measure of AN be obtained. Additional comparisons (Fig. 6b)
show the altered electrode response to be stable over many
measurements.
These included.
Thorough cleaning
restores the original electrode response.

2.5

Run #12 - after

-200

Run #17 - after

-300
-400
-500
-600
0

0.2

0.4

0.6

0.8

1.2

volume of titrant (ml)

(b) Measurements of stearic acid spiked blank solutions
during at intervals during a series of 17 titrations. Two
spiked blank solutions were measured using clean
electrodes before contact of the electrode with crude oil.
A spiked blank solution was remeasured at intervals
between measurements of SQ-95 and Mars-Pink ANs.
Fig. 6. Exposure to crude oil immediately changes the electrode
response. Additional contact with crude oil does not appear to
shift electrode response further. Blank measurements should be
made after crude oil titrations to cancel out changes in electrode
response.

SPE 99884

Acid numbers measured by improved technique. Figure 7

shows AN measured by the improved techniques described
above as a function of oil gravity. Nine percent had AN that
were below the limit of detection (< 0.01 mg KOH/g oil). The
largest number of samples (61%) was between 0.1 and 1; 17%
had AN values greater than 1 mg KOH/g oil. In general,
lower gravity oils had higher values of AN, although the trend
is very scattered. A similarly weak relationships can be found
between log(AN) and the amounts of resins and asphaltenes.
The AN increases with increasing amounts of polar crude oil
components. Crude oil properties are from CO-Wet, a
database of crude oil properties that relate to their wetting
tendencies, described previously.7 The method used to
measure SARA fractions, including resins and nC6
asphaltenes, has also been published previously.8

AN (mg KOH/g oil)

10

0.1

0.01
0

20

40

60

API Gravity ()
Fig. 7. Overall, AN values of 255 crude oils show a decrease with
increasing API gravity.

Interfacial properties correlated with AN. It is widely

believed that ANs are related to low interfacial tensions (IFT)
between some crude oils and displacing brine at sufficiently
alkaline conditions9 although little direct evidence exists either
in laboratory reports10 or field test results11 demonstrating a
direct connection between AN and IFT. The reason often
suggested is that perhaps a small fraction of the acids in a
crude oil may play a large role in IFT reduction, whereas
others may be inactive. Examination of the ASTM method for
measuring AN suggests another alternative: that routine
measurements of AN can be inaccurate, masking any
relationships that might exist between AN and interfacial
properties.
Buckley and Fan12 recently reported that IFT can be
correlated to oil properties, including AN. The correlating
parameters include amount of asphaltene, AN, BN, and
viscosity, with different suites of variables and dependences
for different brine strength and pH conditions.
In alkaline/surfactant processes where a synthetic
surfactant is used to increase oil recovery, phase behavior and
oil/brine IFT depend on many factors, including the relative
amounts of water (containing synthetic surfactant) and oil
(containing natural surfactants).
Zhang and Hirasaki13
observed that optimal salinities (at which IFT is minimized)

could be correlated for a range of water/oil ratios from 1 to 10

by the ratio of natural to synthetic surfactant. Acid number
measured in our laboratory was used in this correlation as the
basis for calculation of the amount of natural surfactant.
While there is more work to be done, these studies suggest
that accurate measurements of AN, together with other crude
oil properties of similar accuracy, can be used to evaluate oils
with respect to their interfacial properties.
Conclusions
Both crude oil and blank solutions must be spiked with an
oil-soluble acid, such as stearic acid, to obtain accurate
and repeatable titration endpoints in non-aqueous
potentiometric titrations to determine AN of crude oils.
Spiking these solutions permits accurate determinations of
AN using smaller samples that those required for the
standard ASTM procedure.
Substitution of tetrabutyl ammonium hydroxide for
potassium hydroxide as titrant confers additional stability
on the titration results.
Methyl isobutyl ketone is not an appropriate substitute for
the standard solvent mixture of toluene/isopropyl
alcohol/water.
Blank measurements must be made after initial crude oil
titrations to compensate for changes in electrode
properties that occur when the electrodes come in contact
with crude oil.
Carefully measured values of AN are reproducible and
correlate with interfacial properties of crude oils.
Acknowledgments
This work was supported by the NPTO office of the US DOE
under contract DE-FC26-01BC15164, by the State of New
Mexico, by industrial sponsors including BP, ChevronTexaco,
and Total. The authors acknowledge the contributions of
Stphanie Monsterleet who first explored adaptations of the
ASTM procedure by spiking crude oils with stearic acid and
helpful discussions with George Hirasaki.
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SPE 99884

Fan, T. and Buckley, J.S.: Rapid and Accurate SARA Analysis

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