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Analyst, June 1995, Vol. 120 1665

Rapid Method for the Determination of Metals


in Lubricating Greases
Published on 01 January 1995. Downloaded by University of Western Ontario on 30/10/2014 03:13:33.

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 Reagents
has been developed. Determination was by AAS. The results
were found to have comparable precision and repeatability All reagents were of analytical-reagent grade from Merck
to those of conventional methods. The method requires only (Elmsford, NY, USA), The reagents comprised: hydrochloric
a simple modification of a glass extraction unit. The relative acid (1.18 g ml-l); nitric acid (1.42 g ml-l); and xylene.
standard deviation was 0.520-0.650% (n = 5). Doubly distilled, de-ionized water was used in all solutions.
Keywords: Lithium determination; extraction; xylene; atomic
absorption spectrometry; lubricating grease 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
Introduction water giving loo0 ppm of Li. Further dilution of this stock
solution was made stepwise avoiding dilutions of more than
Lubricating greases consist of two parts, lubricating oil and a 20-fold.
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 Procedure
determination of metals in greases using mixed solvents.1-7 Preparation of samples
Conventional methods8 for the analysis are indirect, i.e.,
digestion of grease by acid, ashing at 500 4 25 "C and Two commercial-grade greases, A and B, and two IP-grease
dissolving the ash in HCl or extracting the metals (Li, Ca, Na, samples, C and D, were processed (i) as per procedure
etc.) into a dilute hexane-HC1 mixture. These methods are described in IP-199;8 (ii) by a fusion method using Na2C03
time-consuming since metals in grease require extraction into (ACS primary standard grade) in a Pt-crucible and (iii)by our
an aqueous or organic phase prior to analysis. Propionic acid1 method using xylene-HC1 acid as detailed below.
and butyric/isobutyric acid2 have been used as diluents for the
analysis of the oil phase samples. In the present work the Xylene-hydrochloric acid method
sample has been dissolved in xylene and extracted into HCl Prior to preparation of the sample for analysis all the
(1.18 g ml-l). An extraction time of 15 min was sufficient to glassware was thoroughly washed with (1 + 99) H N 0 3
prepare an aqueous solution of the grease sample. +
solution and then with (1 9) HCl solution. The extraction
unit was washed in a similar fashion and then rinsed with
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.

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.
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1666 Analyst, June 1995, Vol. 120

doubly distilled, de-ionized water. Prior to the extraction, 100 Calibration and sample analysis
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 Prior to calibration and analysis the instrument was set up
acid was drained out and the extraction unit was washed with under the conditions given in Table 1and stabilized for 30 min.
de-ionized water ( x 3) before receiving the sample. Lubricat- The stock solution was diluted with doubly distilled, de-
ing grease (0.5-1.0 g) was placed in a 250 ml stoppered conical ionized water to provide 4 , 8 , 12, 16 and 20 ppm Li standard
flask, 50 ml of xylene were added and the flask was warmed in solutions. The dilution factor should be kept below 20 in order
an oven at 50 "C followed by swirling the conical flask for 2 min to keep the error within the permissible limits. The calibration
curve was plotted of concentration, C, (ppm) versus absor-
Published on 01 January 1995. Downloaded by University of Western Ontario on 30/10/2014 03:13:33.

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
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Analyst, June 1995, Vol. 120 1667

interference from other ions is negligible since all such metals 2 Hon P. K., Lan, 0. W., and Mok, C. S., Analyst, 1980, 105,
are seldom present in the same grease. The results obtained 919.
after 30 min of extraction are almost the same as those Holding, S. T., and Noar, J. W., Analyst, 1970, 95, 1041.
obtained after 15 min. The organic layer obtained after 15 min Holding, S. T., and Matthews, P. H. D., Analyst, 1972,97,189.
Holding, S . T., and Rowson, J. J., Analyst, 1975, 100,465.
of extraction was found not to contain any metals. Thus the Psenicnik, O., Nafta (Zagreb) 1988, 39(2), 97.
extraction was complete in 15 min. Additionally, the absence Jain, M. C., Appa Rao, N. V. R., Res. Ind., 1983,28, 133.
of organic matter in the experimental solution keeps the Determination of Lithium and Sodium in Lubricating Grease by
burner clean. Means of Flame Photometer, IP-199, Institute of Petoleum,
Published on 01 January 1995. Downloaded by University of Western Ontario on 30/10/2014 03:13:33.

London.
The authors thank S. Portion for the fabrication of the 9 Salt Content, Crude Petroleum and Products , IP-77/72, Institute
extraction unit. The authors also thank the Director, of the of Petroleum, London.
Indian Institute of Petroleum for permission to publish in- 10 Lead in Gasoline, Volumetric Chromate Method IP-248/71,
Institute of Petroleum, London.
house results of the Institute.

References Paper 4106574C


1 Kabana, M. A., Loseva, D. A., and Turkin, Y. I., Zh. Prikf. Received October 27, 1994
Spectrosk, 1973, 18, 378. Accepted January 9, 1995

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