Talanta 50 (1999) 1135 – 1139


Short communication

pH-Metric method for acid number determination in
hydraulic oils without titration
E. Strochkova, Ya.I. Tur’yan, 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


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
KOH/g [5]) are significantly larger than in trans-
For elimination of the known drawbacks of the former, white or basic oils [4], the reagent for the
standard titration method for acid number (AN) pH-metric AN determination should contain, in
determination in oils alternative pH-metric with- this case, a stronger base in higher concentration.
out titration methods have been developed [1–4]. Therefore, the reagent for vegetable oils [2,3] con-
The methods developed are based on the use of sisted of triethanolamine (TEA) and potassium
special reagents extracting acids from vegetable nitrate in the mixed solvent of water and iso-
[2,3] or some petroleum [4] oils in the iso- propanol was used in the present study. This
propanol–water phase. The sum of the acids is reagent can not be used directly for hydraulic oils
detected in this phase by the pH-metric sensor. [5] which have a number of additives (antioxi-
dants, corrosion inhibitors, viscosity index im-
provers and others [6]) influencing both the glass
* Corresponding author. Tel.: + 972-2-6536534; fax: + 972-
2-6520797. electrode and the process of the acid extraction.
E-mail address: kuselman@netvision.net.il (I. Kuselman) 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

to overcome the matrix effect. The electrodes were introduced into the cell and 2. ter–50% isopropanol (vol.5 B0. which should be stable after approximately 3 min was read. Reagent for the analysis consisted of 0. four replicates per day over five days [3].5 0. The AN calculation is carried out according to sulfuric acid and potassium hydroxide were pur. i. H2SO4 solution is added while stirring (Table 1) and again the conditional pH%2. the AN value is smaller then the meter with a 90. The stirrer was 2. Nst is Hydraulic oils (original Heliar H-24 by stan. 20 ml of heptane were added and then the oil test portion was introduced (Table 1). naries. molecules with carboxylic acids. The Vst volume (Table 1) should be consider- Table 1 Mass of a test portion ably less than the volume of the water–iso- propanol phase (50 ml) [2–4]. n-heptane were from Riedel-de Haën (1) (Seelze. Fortified samples of these oils were H2SO4 solution in ml. Reagents stable for 1 min. Apparatus the conditional pH%1. which should be 2. Expected AN Mass of test portion Addition of 0. a certain volume of the standard 0.3. Israel). the concentration of the standard H2SO4 solution dard [5] and used once) were obtained from Sonol in eqv/l.5–0. The optimal DpH% = pH%1 − pH%2 : 0.3–0. TEA.2.0133. UK). Germany).2) were put into the pH-metric cell.3090. Procedures overcome their interference. Strochko6a et al.3]. TEA+ 0. Vst is the volume of added standard (Haifa. The last component dissolves the oil and its additives and allows us to 2. amides and imidazo.5. potassium chloride. where 56.100 pH%0 − 0. was read. Switzerland) was used as the pH.0726.01 M KNO3 in the solvent of 50% wa- In the present work a heptane-mediated extrac.1.1 N aqueous Ag/AgCl reference electrode. .6 [9] during a day and of np = 20 determination by B0. and nitrogen heterocyclics [8]. If pH%1 \ pH%0 −0.02 of the reagent was properties of the previously developed tri.2–0.01 pH scale and a 6.e. Switzerland).%). and m is the mass of the oil prepared by the addition of naphthenic acid as sample (g). described previously [4].100 limit of quantitation by the technique.3 the proposed new method. Ltd. Germany). polyoxylated amines.e.1136 E. potassium nitrate.11NstVst/m(10DpH% − 1) (mg KOH/g oil) Israel). iso- propanol and toluene from Frutarom (Haifa. and the buffers were from BDH (Poole. i.1 N The experiment for evaluation of the metrologi- for analysis (g) H2SO4 (Vst) (ml) cal parameters consisted of ns = 10 replicate AN determinations by the standard titration method 0. ANB 0. nitrogen quater. Harisau. The initial condi- tion of acids from the oil is proposed to combine tional pH%0 = 11.. Naphthenic acid (EEC hibiting additives [7] such as salts of nitrogenous No 2156628) was purchased from Fluka (Buchs. Experimental turned on to provide good mixing of components.35 should be adjusted. About 50 ml of the reagent for the analysis (see Section 2.2–1 5–1.5 The 632 Metrohm titroprocessor (Metrohm at the max weight of the test portion (5 g).5 0.11 is the molecular mass of KOH. the following expression [2–4]: chased from Merck (Darmstadt. adjusted by addition of KOH traces [2. If pH%1 B glass indicator electrode and a 6. / Talanta 50 (1999) 1135–1139 H or HL (discussed below) have corrosion-in.1.2 M lines. ethanolamine – potassium nitrate – isopropanol– water reagent and heptane. AN= 56.25–0.3 1–3 1.

010 0.17390.11×2× where A is a constant for the given pH-sensor. and r is the correlation coefficient. Ss and Sp the reagent (eqv/l) in the water – isopropanol with fs = ns − 1= 9 and fp = np − 5= 15 numbers phase only. isopropanol – water reagent is characterized in Table 3 shows the average results obtained by Table 2 (b is the slope).010 0. The independence of these and the Student’s ratio t =. Heptane dissolves them and supports the cor- 5 7. portion.016 0.D.11Na(V/m)= 56.999 90.012 1. 10 7. ANmin = 56. This value is suffi- reagent and temperature. E. 10 − 4 × 50/5 = 0. pH% = A −log Na.01 M KNO3 in the solvent of 50% isopropanol–50% H2O in the heptane the results were significantly lower than presence of heptanea by the standard method.999 heptane) that the dependence pH% versus log Na a (Eq. the minimal Na value can also be used dence [1. Strochko6a et al.011 0. of the sum of acids in the reagent in eqv/l. / Talanta 50 (1999) 1135–1139 1137 Table 2 In the attempt to determine AN in hydraulic Parameters of the regression analysis of the dependence pH% oils with the water–isopropanol reagent without vs. The parameters shown in Table 2 of degrees of freedom. (2)) remains linear up to a minimal Na value a is the intercept.013 0. spond to the concentrations of H2SO4 added to corresponding S. The ad- Amount of hep. (2) Therefore.99890.999 rect AN determination.1 mg KOH/g. (1) is derived from the following depen.014 0. but range Na =2 × 10 − 4 }6 ×10 − 3 eqv/l for differ.2]: here for calculation of the minimal AN which is determined correctly by the method ANmin.s of the replicates. [2] (in the absence of 20 7. formally ANmin is not a limit of quantita- The linear dependence pH% versus log Na in the tion (LOQ) as a precision linked value [11.012 0.00890. The values of Na corre.999 oil. the standard ANs and proposed ANp methods. log Na for 50 ml of the reagent: 0.2159 0. Fisher’s ratio F= S 2p/S 2s confirm Eq. Results and discussion phase do not influence this dependence. (2). b is the slope. of 2× 10 − 4 eqv/l. Note.999 It was shown in Ref.99590.2 M TEA+0. it is helpful as the LOQ preliminary assessment or ent amounts of heptane added to 50 ml of the prediction.21290. A possible reason is the additives contained in the hydraulic oils. Na is the concentration cient for the characterization of hydraulic oils. Since. up to 20 ml of heptane added to V= 50 ml of the water–isopropanol 3. A B r2 ditives can cause both glass electrode poisoning tane (ml) and incomplete extraction of the acids from the 0 7.12]. such as the addition of up to m= 5 g of the oil test Eq.2149 0.

ANs − ANp.

freedom. from data [10] at the initial water–iso. However. confidence and fs + fp = 9+15= 24 degrees of ample. it follows that the differ- isopropanol.5. the composition is ods is approximately the same because the differ- 90% heptane. ences between ANp and ANs are insignificant in The reagent volume is not important in the pH. . insignificant (all F-values are less than the critical 51% isopropanol and 2% heptane. From the comparison of these F-data propanol volume 50 ml (50% water and 50% with the critical value.95 level of confidence and the numbers of should be noted that the contact of the water–iso.60 at are practically in the water – isopropanol phase. vol.95 level of composition are insignificantly changed. comparison with the S. of replicates: all t-val- metric AN determination in Eq. For Student’s ratio. means that the salt of TEA and the acid (H2SO4) The critical value for Fisher’s ratio is 2.5% water. For ex./[(S 2s/ parameters from the amount of added heptane ns)+ (S 2p/np)]0.D. propanol and heptane phases their volumes and the critical value is 2.5% isopropanol and 0. It the 0. the one).06). 9. ues are less than the critical value (2. The accuracy of the standard and new meth- heptane phase volume is 21 ml. (1) [2 – 4].06 at the 0.%) and heptane volume 20 ml ence between the repeatability of the results ob- equilibrium volume of the water – isopropanol tained by the standard and the new method is phase is 49 ml and its composition is 47% water. degrees of freedom 9 and 15.

are the average References acid numbers for fortified and initial samples. pp.0106 0. Shenhar. The Proceedings of the Inter- labor consumption. (226.18 95–105 a ANi is the AN of the initial oil sample.). Berlin. are the masses of the initial Talanta 42 (1995) 507.I. national Symposium.20 98. Shenhar.0314 1.D.81 4. spondingly. (mg KOH/g) Recovery (%) Norm of recovery (%) 1 0. New York. (3) where ANf and ANi. mg KOH/g. t is the Student’s ratio. Soc. 260 – 262. Strochkova.46 2 Used 0.0413 2. Tur’yan.600 0. Berezin. the estimated metrological characteris.0586 2.).611 0.Y.55 444. Oil Chem. O. Kogan. ANNA is the average acid num. 218 – 222. The Royal Society of Chemistry. Germany. Strochko6a et al. ANavg is the average acid numbers for fortified samples. 1991.13 4 Fortified 2 2. g.Y.2990 1. O. Shenhar.0218 0. [2] Y. T. 1980.553 0.H.H.92 3 Fortified 1 1. Kuselman. J. / Talanta 50 (1999) 1135–1139 Table 3 Comparison of the results of AN determination by the standard titration method and those obtained by the proposed methoda No.0126 1. Verified Methods Program [3]: the norms shown [6] K. 1985.38 95–105 2 0.0512 2.551 0.51 98. Values of the recovery (Table A. Kuselman.I. determined by pH-metric [1] O. Ogden (Ed. Part 1. Germany.Y.05 a ANs and ANp are the average results obtained by the standard and new methods. A. Chromatographic Science Series. Berlin. G and Q are the masses of the initial oil test portion and naphthenic acid added.52 1. J.I. 4) satisfy the requirements of the AOAC Peer. . respectively. Beuth Verlag GmBH. Marcel Dekker. A.H.Y. Hence. oil sample and the naphthenic acid added.508 0. ber of naphthenic acid determined by titration [4] Y.48 1. Table 4 Determination of recovery for fortified samplesa Sample number ANi (mg KOH/g) G (g) Q (g) ANavg. R(%)= (ANf −ANi)GMNA/(QANNA).1138 E. Tur’yan. F is the Fisher’s ratio. Identification of lubricating points on tics of the pH-metric method are sufficient for the machine tools. Talanta 47 (1998) 53.488 0. the technique including au. MNA =100 is the molecular mass of [3] I.84 1. I. corre. I. Advantages of [8] P. E. L. Hydraulic oils. oils equivalent to the corresponding AN values.1 mg KOH/g). Berezin. AOAC Int. Gouw (Eds. Y.215 0. pp. Oil Sample Standard titration Proposed method F T ANs (mg KOH/g) Ss ANp (mg KOH/g) Sp 1 New 0. G and Q. 73 (1996) 295. Tur’yan.01 1. method.0146 0. Beuth Verlag GmBH.s for these replicates. 81 (1998) 873. I. 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. A. Altgelt. Tur’yan. correspondingly. Shenhar. Kuselman.I. [7] DIN 8659. Kuselman.55 458. Berezin. tomation is simple and inexpensive.41 0. naphthenic acid. quality control of hydraulic oils. Shoenberger for helpful discussion. Berezin. Chromatography in in Table 4 are taken for the contents of acids in Petroleum Analysis. Chemicals in the Oil Industry: Devel- the new method are the following: low time and opments and Applications. Y. vol. 11.203 0. [5] DIN 51 524. London. 1979. O. Ss and Sp are the S.0160 0. Am.

[11] A. . A. Greenberg (Eds. Stan- ucts by semi-micro color indicator titration. 1995.).K. Karapet’yants. . 1995. Wastewater. L. Eaton. ical chemistry. Russian J. An aid to accreditation. 1987. M.I. / Talanta 50 (1999) 1135–1139 1139 [9] Standard test method for acid number of petroleum prod. 19th edn. 41 (1967) 1061. [12] CITAC Guide 1. An American dard Methods for the Examination of Water and National Standard D3339-87. Clesceri. Strochko6a et al.E. 1st edn. Vorob’eva. [10] A. E. International guide to quality in analyt- Chem.S. Phys.D.