Laboratory Experiment

pubs.acs.org/jchemeduc

Determination of Wear Metals in Used Motor Oil by Flame Atomic

Absorption Spectroscopy
Julie A. Palkendo,* Jessica Kovach, and Thomas A. Betts
Department of Physical Sciences, Kutztown University, Kutztown, Pennsylvania 19530, United States
*
S Supporting Information

ABSTRACT: For decades, railways, trucking companies, and commercial airlines

have utilized oil analysis as a diagnostic tool to prevent engine-component failures.
This interesting application was developed into an undergraduate lab experiment to
introduce chemistry and environmental science majors in their second to fourth year
to metal analysis using flame atomic absorption spectroscopy with a non-aqueous
sample matrix. Copper, lead, iron, chromium, and silver were quantified by the
method of standard additions or by external calibration curves with matrix matching.
Students in both environmental analysis and analytical chemistry courses used their
data to assess the health of a vehicle’s engine.

KEYWORDS: Second Year Undergraduate, Upper-Division Undergraduate, Analytical Chemistry, Environmental Chemistry,
Laboratory Instruction, Hands-On Learning/Manipulatives, Applications of Chemistry, Atomic Spectroscopy, Metals,
Quantitative Analysis

Table 1. Wear Metals in Engine Oil2

A s the internal components of an engine spin, whir, and
grind, motor oil is there to lubricate, cool, prevent
corrosion, and disperse dirt. Eventually, the stress of the engine Element Possible Problem with Engine Component
Acceptable
Level/ppm
environment and the buildup of contaminants reduce the Fe Cylinder liner, valve and gear train, oil pump, 100−200
effectiveness of the motor oil, and regular oil changes are rust in system
recommended. Evidence regarding engine wear is contained in Cr Piston ring wear 10−30
the used oil, and many transportation companies (trucking, Cu Bearings and bushing wear 10−50
airline, rail, etc.) invest in extracting this information by Pb Bearing corrosion 40−100
analyzing this oil. Impending engine-component failures can be Al Piston and piston thrust bearing wear 10−30
predicted by higher than normal wear-metal concentrations in Ag Bearing wear 2−5
the used lubricating oil. For example, high levels of chromium Sn Bearing wear 10−30
may indicate excessive wear of piston rings, whereas increases Sia Intake of dirt or sand from a leaking air intake 10−30
in copper and silver concentrations could point to worn system
bearings.1 Metals that are commonly assessed in used oil along Naa Coolant leak varies
with associated engine components2 are highlighted in Table 1. a
Not wear metals, but indicate contamination from external sources.
Typically, used oil from a given engine is analyzed at each oil
change to establish a history of “normal” concentrations of wear
metals for that particular engine. However, in this lab
experiment students rely on the analysis of a single sample The matrix is complex enough to warrant matrix matching of
compared to acceptable metal concentrations, which are based external standards (to maintain similar viscosity) or the method
on statistical analyses of many different engines.3 of standard additions. Although flame atomic absorption (AA)
This laboratory exercise provides a novel and engaging spectroscopy has been used extensively to analyze wear metals
application of atomic spectroscopy, especially for under- in oil samples4−6 and was used in this work, methods are
graduates who may be car enthusiasts. In addition, motor oil available for those who have access to inductively coupled
is an interesting and environmentally relevant matrix that plasma-optical emission spectroscopy (ICP-OES).6−8 This
chemistry or environmental science majors may encounter in situation can provide an excellent opportunity for students to
future careers. A sample of used motor oil can be acquired from appreciate the simultaneous, multielement advantage of ICP-
any vehicle or oil recycling center, and the concentrations of OES over AA.9
wear metals can be easily quantified with straightforward
sample preparation and a basic atomic absorption instrument.
© XXXX American Chemical Society and
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Journal of Chemical Education
Figure 1. Student generated standard addition curves for copper and lead.
Since the 1960s, lab experiments utilizing atomic spectros-
copy have been proposed for the undergraduate chemistry
curriculum10 and continue to be a staple at many colleges and
universities. Most recently, AA experiments have been
published to determine the extent of iron corrosion,11 iron
and calcium in food items,12 various metals in mushrooms,13
and silver in leachate from food storage containers.14 In the
mid-1980s, several educators included AA analysis of lead in
gasoline15,16 by extracting the lead into an aqueous matrix.
Alternatively, the approach described here involves dilution of
an oil sample with a miscible organic solvent prior to AA
analysis. These experiments require analysis of 1−3 wear metals
in used motor oil to evaluate the “health” of an engine. The
methods of standard additions and external calibration curves
with matrix matching were employed in two different chemistry
courses, environmental analysis and advanced analytical
chemistry, with significant positive student feedback. The
environmental analysis course is an introductory analytical
course specifically designed for second- through fourth-year
environmental science majors that are primarily focused in
biology. The advanced analytical chemistry course comprises
predominately second- and third-year chemistry majors.
■ EXPERIMENTAL OVERVIEW
Environmental Analysis
Two lab sections of approximately 14 students each worked in
pairs to analyze a sample of used 10W-30 motor oil from a
1995 Ford F-150 truck. Workstations were set up in fume
hoods and included a shielded, milligram-resolution balance, a
100 μg/g working standard of a 12-element organometallic
standard (SPEX CertiPrep), m-xylene (Fisher Scientific), a
sample of the used motor oil, and disposable glass and plastic
pipets. Students prepared four samples for the method of
standard additions that each contained 2.0 g of the used motor
oil, enough organometallic standard to achieve metal
concentrations ranging from 0−8 ppm, and enough m-xylene
to bring the total mass of the sample to 10 g. The samples were
then sonicated for approximately 5 min. Sample preparation
took students approximately 45 min.
Each student pair selected a wear metal to analyze and with
the help of the instructor, adjusted the operating conditions of a
Varian FS220 AA spectrometer (see the Supporting Informa-
tion). The spectrometer was operated with an air to acetylene
flow ratio of 13.50 to 2.00 L/min, and multielement hollow
cathode lamps were utilized. Students immediately plotted their
absorbance data versus spiked-metal concentration, determined
the original concentration of selected wear metals after
B dx.doi.org/10.1021/ed4004832 | J. Chem. Educ. XXXX, XXX, XXX−XXX
Laboratory Experiment
accounting for dilution, and reported results to the class. The
data analysis and interpretation took approximately 1.5 h for all
student pairs to complete. Students individually prepared
written lab reports and used the compiled class data to predict
engine problems in the Ford F-150 truck.
Advanced Analytical Chemistry
In this course, the motor oil analysis was presented as a project-
based lab option where one pair of students in each of two lab
sections worked for two 3-h lab periods. Students were
provided minimal procedural instructions (see the Supporting
Information); however, they were asked to construct an
external calibration curve using CONOSTAN 75 cSt Blank
Oil (SCP Science), a 12-element organometallic standard, and
solvent. The blank oil was used to maintain a viscosity similar
to that of the used oil sample. The students provided the used
oil samples. These advanced students were also instructed to
quantify at least three wear metals of interest in their used
motor oil samples. Students used instrument manuals and
available literature to develop their procedures and interpret
their results.
■ HAZARDS
Some components of used motor oil are known to be toxic,
carcinogenic, and skin irritants. Therefore, nitrile gloves should
be used to minimize contact between used motor oil and skin.
To control flammable m-xylene vapors during the sample
preparation steps, milligram-resolution balances with draft
shields tall enough to fit sample vials were placed in fume
hoods.
Flammable solvents and flame atomic spectroscopy can be a
hazardous combination, and it is important to follow all
recommended safety practices from the spectrometer’s
manufacturer.17 The drain tube from the nebulizer and waste
container must be composed of materials that are resistant to
organic solvents such as nitrile rubber and glass, respectively.
All samples should remain sealed before analysis and again
immediately after analysis. To minimize solvent evaporation
near the spectrometer flame, vial caps can be replaced with caps
that have a small hole (2−3 mm) drilled in them, through
which to feed the aspirator tubing.
After data collection, the flame should be turned off
according to the manufacturer’s instructions. After the burner
head cools, the liquid trap should be emptied, and the solvent
disposed of properly. The waste container should be emptied
after each laboratory period. Cleaning the liquid trap and spray
chamber after each lab period is also recommended. Disposal of
waste oil and solvent should comply with all regulations.
Journal of Chemical Education
Figure 2. Advanced analytical student generated external calibration curves with matrix matching for copper and lead. These standards and samples
were prepared in a 3:1 ratio of oil to solvent by weight.
■ RESULTS AND DISCUSSION
Figure 1 shows student-generated data in the environmental
analysis lab using the method of standard additions for copper
and lead determinations. The reasonable R2 values (>0.98)
indicate that the students accurately prepared their solutions.
This is important to note because the solutions were prepared
on a weight/weight basis as opposed the more common
weight/volume or volume/volume methods in undergraduate
analytical laboratories. Only 5 out of 27 students executing this
lab experiment reported that they had prepared solutions by
mass more than once before.
After extrapolating the linear regression to the x intercept
and accounting for dilutions, students determined the
concentrations of copper and lead to be 27 and 102 ppm,
respectively. Iron, chromium, and silver were also analyzed.
Iron concentrations ranged from 120 to 180 ppm, and
chromium and silver were not detected. In the students’
assessment of the class results, they concluded that due to
abnormally high lead concentrations a bearing or bushing may
need to be replaced in the Ford F-150 engine.
In the project-based version of this experiment, the advanced
analytical students were challenged to think critically about how
experimental design factors such as selection of the standard
concentration range, multiple measurements, and sample
preparation relate to the data quality parameters of linearity,
reproducibility, and sensitivity. Figure 2 shows external
calibration curves with matrix matching to analyze the used
motor oil of a student’s 1998 Nissan Maxima. Correlation
coefficients of >0.98 were obtained, and the concentrations of
copper, lead, and chromium were 2.0, 7.8, and 2.7 ppm,
respectively. The student was relieved to learn that the oil
analysis did not indicate any problems with the Nissan’s engine
components.
Twenty-seven students in the environmental analysis course
were surveyed after executing the experiment, and 24 ranked
the experiment as either interesting or very interesting.
Additionally, 20 students found the experience to be highly
applicable to their environmental science major. Students
commented that they did not know this type of analysis was
performed and were intrigued to learn about the chemistry
behind regular vehicle maintenance. Some students were
disappointed that they did not get to analyze their own
vehicle’s motor oil, and some suggested testing recycled oil and
used motor oil after x, y, and z miles driven on their vehicles.
Overall, the feedback confirmed that students were fully
engaged in the experiment and understood the chemical
relevance of the analysis.
C dx.doi.org/10.1021/ed4004832 | J. Chem. Educ. XXXX, XXX, XXX−XXX
Laboratory Experiment
■
*
ASSOCIATED CONTENT
S Supporting Information
Student handouts for both courses; instructor notes. This
material is available via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*Corresponding Author Email: palkendo@kutztown.edu.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors wish to thank the students in the spring 2013
courses of CHM/ENV220 and CHM340 for their participation
and valuable feedback.
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