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The Analysis of Coal Tar Pitch

by ICP Optical Emission Spectrometry
After Digestion in a Microwave Oven System
Maryanne Thomsen
Perkin Elmer European ICP Support Group, Hansa Allee 195, D-40549 Duesseldorf, Germany
and
Peter Kainrath
Bodenseewerk Perkin Elmer GmbH, P.O. Box 10 17 61, D-88647 Überlingen, Germany

INTRODUCTION coupled plasma optical emission In the work presented here,

spectrometry (ICP-OES). The approximately 200 mg of the sam-
Tar and pitch are materials method of destruction and of mea- ple was accurately weighed into the
used in modern organic chemistry surement is described in full and quartz vessels of the Perkin-Elmer
as base products for a number of some results for a reference coal tar Multiwave microwave digestion
heterocyclic compounds in addi- pitch sample are presented. system (Perkin-Elmer, Norwalk, CT
tion to many other industrial uses. USA). To each sample, 5 mL of
Pitch can be used for electrodes in SAMPLE PREPARATION concentrated (65%) HNO3 (Merck®
the production of aluminum, for Suprapur) was added. For each run
example. For such applications, the Microwave-assisted digestion of the programs, at least one of the
product must be specified and the procedures are becoming more vessels contained acid only for a
specification adhered to at all times. popular as they considerably sample blank. The samples were
The samples can be viscous liquids reduce the amount of time spent digested using the program listed
or black solids. They are difficult preparing the sample for the spec- in Table I.
samples to analyze for their inor- trometric analysis. Due to the
ganic components because of their nature of the heating process in Phase 1 ramps the unpulsed
complex chemical structure. Usu- microwave-assisted digestion, sev- power from 100 W to 600 W over
ally the analysis of the major eral precautions have to be consid- a period of 30 minutes. Phase 2
elements is sufficient; however, ered before digesting a sample of maintains this power level for an
when the material is for industrial high reactivity like tar and pitch. additional 10 minutes. Phase 3 is
use, a full and accurate analysis is The following considerations have a cooling phase where the micro-
often required. to be made: wave power is turned off and the
fan speed increased to effect rapid
Theoretically, the samples could • What happens to the sample cooling of the sample. Once the
be dissolved in an organic solvent if it is exposed to microwave system has reached the maximum
and aspirated into the atomic spec- radiation? operating pressure of 75 bar (1125
trometer. In practice, the high vis- psi), the microwave power is
• What is the maximum sample
cosity and complex nature of the reduced to the level necessary to
weight the digestion system
samples means that they are not maintain a continuous operating
can handle?
very soluble and the results with pressure of 72 bar (1080 psi),
this method are not of the required • Are any spontaneous reactions a level at which the maximum
standard. The samples must there- expected? digestion temperature is reached
fore be digested in acid prior to (see Figure 1).The whole program
analysis. This step takes consider- In addition to the reaction condi-
tions, the instrumental parameters takes 55 minutes, after which the
ably longer than the ICP analysis vessels can be opened, and the
and can become the bottleneck in have to be checked as well, such as:
clear, colorless digest can be
the laboratory. It is also very labor- • Ramping up the microwave washed into a 25-mL flask and
intensive unless a technique like power to ensure controlled diluted to the mark with water.
microwave digestion is employed chemical reactions.
to automate the procedure. The TABLE I
samples also contain a very great • Safety measures in case of spon-
taneous or vigorous chemical Microwave Digestion Program
deal of carbon, making their com-
plete digestion more difficult. reactions. Phase Power Time Power Fan
(min) (W) (W) speed
A method has been developed • Maximum temperature and pres-
sure tolerance of the equipment. 1 100 30 600 1
where samples of tar and pitch can
be digested easily and analyzed in 2 600 10 600 1
• Available vessel materials of the
little over an hour by inductively required degree of cleanliness. 3 0 15 0 3

AS Atomic Spectroscopy
Vol. 19(2), March/April 1998
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 AStomic
pectroscopy
Vol. 19(2), Mar./Apr. 1998

The final acid concentration in

the prepared samples is then
20% HNO3.

MEASUREMENT PARAMETERS
The samples were analyzed using
a Perkin-Elmer Optima 3000™
radial inductively coupled plasma
optical emission spectrometer
(ICP-OES). The ICP system was
calibrated with the Merck IV multi-
element standard at 10 mg/L and
some standards were prepared
from single-element solutions. The
calibration was checked with the
PE Pure Atomic Spectroscopy Cali-
bration Verification standard. All
standards were prepared in a Fig. 1. Multiwave Digestion Procedure.
matrix of 20% HNO3.
The compromise plasma condi- element (mg/Kg) and major TABLE II
tions for the Optima 3000 ICP-OES, element (g/Kg) concentrations can Instrumental Parameters
equipped with a GemTip™ cross- be determined on the same sample
Plasma gas 15 L/min
flow nebulizer and Ryton™ spray solution without the need for dilu-
tions. Auxiliary gas 0.5 L/min
chamber, were used without any
attempt to optimize the system. Nebulizer gas 0.9 L/min
The instrumental parameters are CONCLUSION Power 1200 W
listed in Table II. The solutions are clear after the Viewing height 10 mm above
digestion procedure and are simply the load coil
RESULTS made up to the final volume with Sample uptake 1 mL/min
The results were measured in deionized water and analyzed on
mg/L in solution and converted to the ICP.
Table III
mg/Kg in the solid sample by enter- The high pressure of the Results for Domtar Certified
ing the sample weight taken and microwave oven and gentle ramp- Reference Coal Tar Pitch
final volume into the Optima soft- ing of the power help to digest the Sample, Measured Values
ware. The results obtained for a sample without any losses and to Compared with
Domtar certified reference material remove most of the carbon in the Certified Values in mg/Kg
are listed in Table III. sample. The residual carbon levels
Certified Found
The values obtained agree well are minimal as can be seen from the Element (mg/Kg) (mg/Kg)
and are within two standard devia- clearness of the solutions. Partially
digested solutions tend to give a Al 245(7) 243.8
tions of the certified values in all
cases. No systematic bias is yellow colored solution. Also, a Ca 95(18) 93.2
observed indicating that there are high carbon content can lead to Cr 0.94(0.07) 0.979
no significant matrix effects. unwanted background peaks in the Fe 208(13) 213
ICP and to density and surface ten-
For each analyte element, a sen- sion effects. This causes the solu- Na 286(24) 318
sitive emission line free from spec- tion to aspirate at a different rate to Ni 2.6(0.3) 2.75
tral interferences was available. the standards and thus introduces P 10(2) 10.5
Therefore, no overlap corrections error into the analysis. Pb 91(6) 108
were necessary. Simple one- or two-
The process of sample decompo- S 4900(300) 5187
point background correction was
sufficient in every case. sition followed by ICP analysis takes V 1.33(0.07) 1.5
little over an hour and both the Zn 91(12) 91.1
The very wide working range is microwave system and the ICP-OES
a feature of ICP analysis and trace can be left to work unattended. ( )=The values in parentheses are the
uncertainties.

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