Talanta 50 (1999) 1135 1139

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Short communication

pH-Metric method for acid number determination in

hydraulic oils without titration
E. Strochkova, Ya.I. Turyan, I. Kuselman *
The National Physical Laboratory of Israel, Gi6at Ram, Jerusalem 91904, Israel

Received 26 February 1999; received in revised form 14 June 1999; accepted 24 June 1999

Abstract

A heptane-mediated extraction of acids from hydraulic oils is proposed for pH-metric acid number determination
without titration. The acids are extracted in the reagent consisting of triethanolamine and potassium nitrate dissolved
in water and isopropanol. The use of heptane allows us to overcome the influence of additives in the hydraulic oil on
the glass electrode. Simultaneously the extraction of acids from the oil into the water isopropanol phase is simplified.
The method is validated and suitable metrological characteristics of the acid number determination are obtained.
Published by Elsevier Science B.V.

Keywords: Acid number; pH-Metry; Hydraulic oils; Metrological parameters

1. Introduction Since AN values in hydraulic oils (AN\ 0.3 mg

For elimination of the known drawbacks of the
standard titration method for acid number (AN)
determination in oils alternative pH-metric with-
out titration methods have been developed [14].
The methods developed are based on the use of
special reagents extracting acids from vegetable
[2,3] or some petroleum [4] oils in the iso-
propanolwater phase. The sum of the acids is
detected in this phase by the pH-metric sensor.
* Corresponding author. Tel.: + 972-2-6536534; fax: + 972-
2-6520797.
E-mail address: kuselman@netvision.net.il (I. Kuselman)
KOH/g [5]) are significantly larger than in trans-
former, white or basic oils [4], the reagent for the
pH-metric AN determination should contain, in
this case, a stronger base in higher concentration.
Therefore, the reagent for vegetable oils [2,3] con-
sisted of triethanolamine (TEA) and potassium
nitrate in the mixed solvent of water and iso-
propanol was used in the present study. This
reagent can not be used directly for hydraulic oils
[5] which have a number of additives (antioxi-
dants, corrosion inhibitors, viscosity index im-
provers and others [6]) influencing both the glass
electrode and the process of the acid extraction.
For example, hydraulic oils specified by symbols

0039-9140/99/$ - see front matter Published by Elsevier Science B.V.

PII: S 0 0 3 9 - 9 1 4 0 ( 9 9 ) 0 0 1 9 2 - 7
1136 E. Strochko6a et al. / Talanta 50 (1999) 11351139
H or HL (discussed below) have corrosion-in-
hibiting additives [7] such as salts of nitrogenous
molecules with carboxylic acids, nitrogen quater-
naries, polyoxylated amines, amides and imidazo-
lines, and nitrogen heterocyclics [8].
In the present work a heptane-mediated extrac-
tion of acids from the oil is proposed to combine
properties of the previously developed tri-
ethanolamine potassium nitrate isopropanol
water reagent and heptane. The last component
dissolves the oil and its additives and allows us to
overcome their interference, i.e. to overcome the
matrix effect.
2. Experimental
2.1. Apparatus
The 632 Metrohm titroprocessor (Metrohm
Ltd., Harisau, Switzerland) was used as the pH-
meter with a 90.01 pH scale and a 6.0133.100
glass indicator electrode and a 6.0726.100
aqueous Ag/AgCl reference electrode.
2.2. Reagents
TEA, potassium nitrate, potassium chloride,
sulfuric acid and potassium hydroxide were pur-
chased from Merck (Darmstadt, Germany), iso-
propanol and toluene from Frutarom (Haifa,
Israel), n-heptane were from Riedel-de Haen
(Seelze, Germany), and the buffers were from
BDH (Poole, UK).
Hydraulic oils (original Heliar H-24 by stan-
dard [5] and used once) were obtained from Sonol
(Haifa, Israel). Fortified samples of these oils were
prepared by the addition of naphthenic acid as
Table 1
Mass of a test portion
Expected AN Mass of test portion Addition of 0.1 N
for analysis (g) H2SO4 (Vst) (ml)
0.21 51.5 0.20.3
13 1.50.5 0.30.6
\3 B0.5 B0.3
described previously [4]. Naphthenic acid (EEC
No 2156628) was purchased from Fluka (Buchs,
Switzerland).
Reagent for the analysis consisted of 0.2 M
TEA+ 0.01 M KNO3 in the solvent of 50% wa-
ter50% isopropanol (vol.%). The initial condi-
tional pH%0 = 11.3090.02 of the reagent was
adjusted by addition of KOH traces [2,3].
2.3. Procedures
About 50 ml of the reagent for the analysis (see
Section 2.2) were put into the pH-metric cell, 20
ml of heptane were added and then the oil test
portion was introduced (Table 1). The stirrer was
turned on to provide good mixing of components.
The electrodes were introduced into the cell and
the conditional pH%1, which should be stable after
approximately 3 min was read. If pH%1 \ pH%0 0.5
at the max weight of the test portion (5 g),
ANB 0.1, i.e. the AN value is smaller then the
limit of quantitation by the technique. If pH%1 B
pH%0 0.5, a certain volume of the standard 0.1 N
H2SO4 solution is added while stirring (Table 1)
and again the conditional pH%2, which should be
stable for 1 min, was read. The optimal DpH% =
pH%1 pH%2 : 0.250.35 should be adjusted.
The AN calculation is carried out according to
the following expression [24]:
AN= 56.11NstVst/m(10DpH% 1) (mg KOH/g oil)
(1)
where 56.11 is the molecular mass of KOH, Nst is
the concentration of the standard H2SO4 solution
in eqv/l, Vst is the volume of added standard
H2SO4 solution in ml, and m is the mass of the oil
sample (g).
The Vst volume (Table 1) should be consider-
ably less than the volume of the wateriso-
propanol phase (50 ml) [24].
The experiment for evaluation of the metrologi-
cal parameters consisted of ns = 10 replicate AN
determinations by the standard titration method
[9] during a day and of np = 20 determination by
the proposed new method, four replicates per day
over five days [3].
 E. Strochko6a et al. / Talanta 50 (1999) 11351139 1137

Table 2 In the attempt to determine AN in hydraulic

Parameters of the regression analysis of the dependence pH%
oils with the waterisopropanol reagent without
vs. log Na for 50 ml of the reagent: 0.2 M TEA+0.01 M
KNO3 in the solvent of 50% isopropanol50% H2O in the heptane the results were significantly lower than
presence of heptanea by the standard method. A possible reason is the
additives contained in the hydraulic oils. The ad-
Amount of hep- A B r2 ditives can cause both glass electrode poisoning
tane (ml)
and incomplete extraction of the acids from the
0 7.21290.012 0.99590.010 0.999 oil. Heptane dissolves them and supports the cor-
5 7.17390.012 1.00890.010 0.999 rect AN determination.
10 7.2149 0.016 0.999 90.013 0.999 It was shown in Ref. [2] (in the absence of
20 7.2159 0.014 0.99890.011 0.999 heptane) that the dependence pH% versus log Na
a
(Eq. (2)) remains linear up to a minimal Na value
a is the intercept, b is the slope, and r is the correlation
coefficient. of 2 10 4 eqv/l. Since, up to 20 ml of heptane
added to V= 50 ml of the waterisopropanol
3. Results and discussion phase do not influence this dependence, such as
the addition of up to m= 5 g of the oil test
Eq. (1) is derived from the following depen- portion, the minimal Na value can also be used
dence [1,2]: here for calculation of the minimal AN which is
determined correctly by the method ANmin.
pH% = A log Na, (2) Therefore, ANmin = 56.11Na(V/m)= 56.112
where A is a constant for the given pH-sensor, 10 4 50/5 = 0.1 mg KOH/g. This value is suffi-
reagent and temperature; Na is the concentration cient for the characterization of hydraulic oils.
of the sum of acids in the reagent in eqv/l. Note, formally ANmin is not a limit of quantita-
The linear dependence pH% versus log Na in the tion (LOQ) as a precision linked value [11,12], but
range Na =2 10 4 }6 10 3 eqv/l for differ- it is helpful as the LOQ preliminary assessment or
ent amounts of heptane added to 50 ml of the prediction.
isopropanol water reagent is characterized in Table 3 shows the average results obtained by
Table 2 (b is the slope). The values of Na corre- the standard ANs and proposed ANp methods,
spond to the concentrations of H2SO4 added to corresponding S.D.s of the replicates, Ss and Sp
the reagent (eqv/l) in the water isopropanol with fs = ns 1= 9 and fp = np 5= 15 numbers
phase only. The parameters shown in Table 2 of degrees of freedom, Fishers ratio F= S 2p/S 2s
confirm Eq. (2). The independence of these
parameters from the amount of added heptane
means that the salt of TEA and the acid (H2SO4)
are practically in the water isopropanol phase. It
should be noted that the contact of the wateriso-
propanol and heptane phases their volumes and
composition are insignificantly changed. For ex-
ample, from data [10] at the initial wateriso-
propanol volume 50 ml (50% water and 50%
isopropanol, vol.%) and heptane volume 20 ml
equilibrium volume of the water isopropanol
phase is 49 ml and its composition is 47% water,
51% isopropanol and 2% heptane. However, the
heptane phase volume is 21 ml, the composition is
90% heptane, 9.5% isopropanol and 0.5% water.
The reagent volume is not important in the pH-
metric AN determination in Eq. (1) [2 4].
and the Students ratio t =ANs ANp/[(S 2s/
ns)+ (S 2p/np)]0.5.
The critical value for Fishers ratio is 2.60 at
the 0.95 level of confidence and the numbers of
degrees of freedom 9 and 15. For Students ratio,
the critical value is 2.06 at the 0.95 level of
confidence and fs + fp = 9+15= 24 degrees of
freedom. From the comparison of these F-data
with the critical value, it follows that the differ-
ence between the repeatability of the results ob-
tained by the standard and the new method is
insignificant (all F-values are less than the critical
one). The accuracy of the standard and new meth-
ods is approximately the same because the differ-
ences between ANp and ANs are insignificant in
comparison with the S.D. of replicates: all t-val-
ues are less than the critical value (2.06).
1138 E. Strochko6a et al. / Talanta 50 (1999) 11351139

Table 3
Comparison of the results of AN determination by the standard titration method and those obtained by the proposed methoda

No. Oil Sample Standard titration Proposed method F T

ANs (mg KOH/g) Ss ANp (mg KOH/g) Sp

1 New 0.553 0.0106 0.551 0.0126 1.41 0.46

2 Used 0.611 0.0160 0.600 0.0146 0.84 1.92
3 Fortified 1 1.215 0.0314 1.203 0.0218 0.48 1.13
4 Fortified 2 2.488 0.0413 2.508 0.0586 2.01 1.05

a
ANs and ANp are the average results obtained by the standard and new methods, respectively; Ss and Sp are the S.D.s for these
replicates; F is the Fishers ratio; t is the Students ratio.

Table 4
Determination of recovery for fortified samplesa

Sample number ANi (mg KOH/g) G (g) Q (g) ANavg, (mg KOH/g) Recovery (%) Norm of recovery (%)

1 0.55 444.52 1.2990 1.20 98.38 95105

2 0.55 458.81 4.0512 2.51 98.18 95105

a
ANi is the AN of the initial oil sample; G and Q are the masses of the initial oil test portion and naphthenic acid added; ANavg
is the average acid numbers for fortified samples.

The recovery (Table 4) was determined for all Acknowledgements

fortified samples in accordance to the following
formula: The authors would like to express their grati-
tude to Professor E. Shoenberger for helpful
discussion.
R(%)= (ANf ANi)GMNA/(QANNA), (3)

where ANf and ANi, mg KOH/g, are the average References

acid numbers for fortified and initial samples,
correspondingly, determined by pH-metric
method; G and Q, g, are the masses of the initial
oil sample and the naphthenic acid added, corre-
spondingly; MNA =100 is the molecular mass of
naphthenic acid; ANNA is the average acid num-
ber of naphthenic acid determined by titration
(226.1 mg KOH/g). Values of the recovery (Table
4) satisfy the requirements of the AOAC Peer-
Verified Methods Program [3]: the norms shown
in Table 4 are taken for the contents of acids in
oils equivalent to the corresponding AN values.
Hence, the estimated metrological characteris-
tics of the pH-metric method are sufficient for the
quality control of hydraulic oils. Advantages of
the new method are the following: low time and
labor consumption, the technique including au-
tomation is simple and inexpensive.
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 E. Strochko6a et al. / Talanta 50 (1999) 11351139 1139

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