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Analyst, June 1995, Vol. 120 1665

Rapid Method for the Determination of Metals

in Lubricating Greases
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The late Silas F. Fish and Rakesh K. Chauhan

Indian Institute of Petroleum, Dehradun-248 005, India

A method for the rapid determination of the metal content in Chemicals

lubricating greases using xylenehydrochloric acid extraction
has been developed. Determination was by AAS. The results
were found to have comparable precision and repeatability
to those of conventional methods. The method requires only
a simple modification of a glass extraction unit. The relative
standard deviation was 0.520-0.650% (n = 5).
Keywords: Lithium determination; extraction; xylene; atomic
absorption spectrometry; lubricating grease
Introduction
Lubricating greases consist of two parts, lubricating oil and a
metallic soap. Soaps are generally used as thickening agents.
Greases are not soluble in hydrophobic or hydrophilic
solvents. Many workers have applied direct analysis to the
determination of metals in greases using mixed solvents.1-7
Conventional methods8 for the analysis are indirect, i.e.,
digestion of grease by acid, ashing at 500 4 25 "C and
dissolving the ash in HCl or extracting the metals (Li, Ca, Na,
etc.) into a dilute hexane-HC1 mixture. These methods are
time-consuming since metals in grease require extraction into
an aqueous or organic phase prior to analysis. Propionic acid1
and butyric/isobutyric acid2 have been used as diluents for the
analysis of the oil phase samples. In the present work the
sample has been dissolved in xylene and extracted into HCl
(1.18 g ml-l). An extraction time of 15 min was sufficient to
prepare an aqueous solution of the grease sample.
Experimental
Apparatus
An atomic absorption spectrometer (Pye Unicam, Cambridge
PU-9000) fitted with appropriate hollow cathode lamps (Li,
Ca, Na, etc.) and a flame emission spectrometer (Eppendorf,
Germany) were used.
Reagents
All reagents were of analytical-reagent grade from Merck
(Elmsford, NY, USA), The reagents comprised: hydrochloric
acid (1.18 g ml-l); nitric acid (1.42 g ml-l); and xylene.
Doubly distilled, de-ionized water was used in all solutions.
Stock solution
A stock solution of Li was made by dissolving 5.3240 g of
Li2C03, [99.997%] in lo00 ml of doubly distilled, de-ionized
water giving loo0 ppm of Li. Further dilution of this stock
solution was made stepwise avoiding dilutions of more than
20-fold.
Procedure
Preparation of samples
Two commercial-grade greases, A and B, and two IP-grease
samples, C and D, were processed (i) as per procedure
described in IP-199;8 (ii) by a fusion method using Na2C03
(ACS primary standard grade) in a Pt-crucible and (iii)by our
method using xylene-HC1 acid as detailed below.
Xylene-hydrochloric acid method
Prior to preparation of the sample for analysis all the
glassware was thoroughly washed with (1 + 99) H N 0 3
+
solution and then with (1 9) HCl solution. The extraction
unit was washed in a similar fashion and then rinsed with

Mufle Furnace
The muffle furnace was suitably lagged to attain a uniform
temperature of 500 k 25°C.

Extraction unit
A modified form of the IP-779/IP-24810 extraction unit of
Pyrex glass as shown in Fig. 1was fabricated in the laboratory. /1000 rnd
The dimensions, heating wire and the other requirements
conform to IP-248 except that, in our unit, the condenser and
the flask could be separated by a B 24/29 cone and socket joint
so that the condenser can be cleaned thoroughly with ease.

Other equipment
A platinum crucible (capacity 25 ml) with a lid was used.
Glassware was from BorosiYCorning (Corning, NY, USA). Fig. 1 Extraction apparatus.
 View Article Online

1666 Analyst, June 1995, Vol. 120

doubly distilled, de-ionized water. Prior to the extraction, 100
ml of (1 + 9) HCI was boiled in the extraction unit for 0.5 h and
the solution was analysed, thus providing a blank run. The
acid was drained out and the extraction unit was washed with
de-ionized water ( x 3) before receiving the sample. Lubricat-
ing grease (0.5-1.0 g) was placed in a 250 ml stoppered conical
flask, 50 ml of xylene were added and the flask was warmed in
an oven at 50 "C followed by swirling the conical flask for 2 min
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Calibration and sample analysis
Prior to calibration and analysis the instrument was set up
under the conditions given in Table 1and stabilized for 30 min.
The stock solution was diluted with doubly distilled, de-
ionized water to provide 4 , 8 , 12, 16 and 20 ppm Li standard
solutions. The dilution factor should be kept below 20 in order
to keep the error within the permissible limits. The calibration
curve was plotted of concentration, C, (ppm) versus absor-

until mixing was complete. The solution was transferred into

the extraction unit. The conical flask was rinsed with warm bance. The sample reading was taken directly after approp-
xylene (X3) and the xylene was poured into the same riate dilution. Since the samples did not contain any contami-
extraction unit. The total amount of xylene used was 250 ml. nants no ionization suppressant was added. Suitable
After addition of 25 ml of HCI to the grease-xylene mixture, precautions are necessary if contaminants are expected to be
the solution was heated to its boilig point. The extraction was present. The sample value is obtained by calculating the linear
carried for ( i ) 30 rnin or (ii) 15 rnin duration each. Each grease regression of a plot of the concentration (in ppm) versus the
sample was processed in five sets for the determination of Li, absorbance. The concentration of the sample was obtained by
giving 10 solutions. Heating was stopped for 1rnin to allow the multiplying this reading by the dilution factor. All the
acid layer to settle. It was then drained into a clean beaker. measurements were made on an atomic absorption spec-
The organic layer was also tested for the presence of Li metal trometer (PU-9OOO). A flame emission spectrometer (Eppen-
to establish whether the extraction was complete. The dorf) was used for samples analysed by the IP-199 procedure.
extraction unit was washed with 50 ml of doubly distilled, de- For samples obtained by the Na2C03 fusion method, matrix
ionized water which was boiled for a further 5 rnin after which matching was obtained between standards and the sample by
the water layer was drained into the beaker. The contents of putting a calculated amount of Na2C03 in both solutions.
the beaker were boiled for 10 rnin to reduce the acid content.
Then the material was transferred into a 100 ml calibrated Results and Discussion
flask and diluted to volume with doubly distilled, de-ionized
water. The results are compiled in Table 2. The equation of the
calibration curve is C = 40.63312~-0.1411753 (where x =
~~~~~~~
absorbance value), r = 0.9995856 and the F-test ratio is
7238.765. The xylene-HCl method provides precise and
Table 1 Instrumental conditions for the PU-9OOO atomic absorption
spectrometer for lithium determination repeatible results when compared with other methods (IP-199
and Na2C03). The coefficient of determination shows that the
Wavelengt h/nm 670.8 results obtained from the xylene-HC1 method are within the
Slit widthhm 0.5 98% confidence level. The relative standard deviation indi-
Pressure of air/kPa 207 cates that there is very little variance in the results. The
Flame used Air-Acetylene extraction is easy to perform with a low chance of manual
Pressure of acetylene/kPa 83 error. Since the grease is very easily miscible in warm xylene,
Flow rate of fueVl min-l 0.8 extraction of metals from the grease with the concentrated
Lamp current/mA 7.5 HCI is easy. This extraction method can be used for the
Analysis time/s 4.0
Scale factor 1.0 comprehensive determination of metals because HCl can
extract many metals from the grease. The possibility of

Table 2 Lithium determination in greases. Comparison of Various Methods

Xylene-HC1 extraction method

30 rnin 15 rnin IP-199 Na2C03fusion

method method
C Relative mean C Relative mean C C
Sample (ppm) s deviation (%) s, (PPm) s deviation (%) s, (PP4 (PPm)
A 2953 2930
2961 2950 2897
3003 14.04 0.472 0.65 2900 14.40 0.491 0.677 2900 2900
2965 2940
2975 2945
B 2927 2900
2900 2880 2850
2890 13.92 0.477 0.565 2850 12.4 0.43 0.685 2800 2825
2920 2875
2925 2885
C 1890 1870 1855
1870 8.8 0.467 0.541 1875 12.0 0.637 0.671 1850 1860
1880 1900
1880 1880
1900 1900
D 3460 3490 3450
3430 15.2 0.439 0.520 3480 16.8 0.485 0.535 3450 3465
3480 3450
3475 3460
3450 3440

interference from other ions is negligible since all such metals
are seldom present in the same grease. The results obtained
after 30 min of extraction are almost the same as those
obtained after 15 min. The organic layer obtained after 15 min
of extraction was found not to contain any metals. Thus the
extraction was complete in 15 min. Additionally, the absence
of organic matter in the experimental solution keeps the
burner clean.
Published on 01 January 1995. Downloaded by University of Western Ontario on 30/10/2014 03:13:33.
The authors thank S. Portion for the fabrication of the
extraction unit. The authors also thank the Director, of the
Indian Institute of Petroleum for permission to publish in-
house results of the Institute.
References
1 Kabana, M. A., Loseva, D. A., and Turkin, Y. I., Zh. Prikf.
Spectrosk, 1973, 18, 378.
View Article Online
Analyst, June 1995, Vol. 120 1667
2 Hon P. K., Lan, 0. W., and Mok, C. S., Analyst, 1980, 105,
919.
Holding, S. T., and Noar, J. W., Analyst, 1970, 95, 1041.
Holding, S. T., and Matthews, P. H. D., Analyst, 1972,97,189.
Holding, S . T., and Rowson, J. J., Analyst, 1975, 100,465.
Psenicnik, O., Nafta (Zagreb) 1988, 39(2), 97.
Jain, M. C., Appa Rao, N. V. R., Res. Ind., 1983,28, 133.
Determination of Lithium and Sodium in Lubricating Grease by
Means of Flame Photometer, IP-199, Institute of Petoleum,
London.
9 Salt Content, Crude Petroleum and Products , IP-77/72, Institute
of Petroleum, London.
10 Lead in Gasoline, Volumetric Chromate Method IP-248/71,
Institute of Petroleum, London.
Paper 4106574C
Received October 27, 1994
Accepted January 9, 1995