a t 52 "C with trifluoroacetic anhydride in dry benzene to in the spectrum corresponded to the molecular weight of

produce 111. Using these smaller amounts, the yield of the the desired product. Further proof of identity came from
reaction averaged 85%. studying the fragmentation patterns, which in general were
To determine if the derivatization reactions might be similar to other substituted ureas (15).
adapted to other urea herbicides, diuron, fenuron, and The studies reported here suggest that derivatization
monuron were studied. All three were successfully reacted reactions can be performed on trisubstituted ureas to form
with methyl iodide to produce the trimethylated com- products with enhanced thermal stability and increased
pounds. However, only fenuron and monuron reacted with sensitivity of detection. Such derivatives should be useful
trifluoroacetic anhydride. The reaction conditions were not for developing sensitive analytical procedures for these
optimized and as a result, yields were poor. Only the pres- compounds.
ence or absence of a product was noted on the chromato-
gram. In the five successful reactions on diuron, fenuron, ACKNOWLEDGMENT
and monuron, the expected product was obtained and was The authors thank E. W. Day and J. W. Mosier for their
found to be stable under the conditions used during GC. assistance and suggestions.
The identity of these products was confirmed by GC-MS.
Combined GC-MS was used as the primary identifica- Received for review October 1, 1973. Accepted April 24,
tion tool for all derivatives prepared in these various exper- 1974.
iments. This instrument proved to be ideal for such work;
only a small amount of compound was required, extensive
sample preparation was unnecessary, and spectra took only (15) M. A . Baldwin, A. M. Kirkien-Konasiewicz, A. G. Loudon, A . Maccoll. and
a few seconds each to record. In all cases, the molecular ion D. Smith, J. Chem. SOC.B, 1968, 34.

Determination of Fluoride in Coal with the Fluoride

Ion-Selective Electrode

Josephus Thomas, Jr., and Harold J. Gluskoter

iiiinois State Geoiogicai Survey. Urbana. 111. 6180 1

Fluorine is one of several trace elements in coal current- a t the time were unsuitable for the determination of fluo-
ly receiving much attention owing to their possible harmful rine in coal, Crossley selected and modified a method that
ecological effects upon being released from the large ton- depends on the fading action fluorides have on zirconium-
nages of coal being burned annually. As those engaged in alizarin lake. In his method, the coal is decomposed. ei-
coal analysis recognize, the determination of trace ele- ther in a combustion bomb or by alkali ignition, and the
ments with satisfactory accuracy and precision is difficult, fluoride is separated by distillation as fluosilicic acid. The
not only because of the heterogeneity of the material but fluoride content of British coals. sampled from widespread
also because of the lack of coal standards. locations, was found to range from 5 t o 200 ppm.
Until the invention of the fluoride ion-selective elec- The method we describe here requires no separations.
trode by Frant and Ross ( I ) a few years ago, fluorine anal- Coal samples are decomposed in a combustion bomb, the
ysis, particularly at the parts-per-million level, was a pH of the bomb contents is adjusted, and the solution is
challenge for the analyst. Among the problems associated buffered prior to the determination of the fluoride concen-
with fluorine analysis, mention may be made of the action tration with the fluoride ion-selective electrode. Analysis
of fluorides on glassware. the high solubility of nearly all is by the known addition method (6) in which the change
fluorides thereby eliminating gravimetric methods, and of potential (1.E) resulting from the addition of a known
the complexing of fluorides by iron, aluminum. and cer- volume of standard fluoride solution to the initial test so-
tain other cations in solution. Today, however, the use of lution is used to determine the fluoride concentration of
the fluoride ion-selective electrode is commonplace for the the initial solution. This technique is superior to direct
reliable determination of fluoride at quite low (10-5 LO potentiometry as problems resulting from interferences.
10--6M) concentration (activity) levels. In many cases, complexation, and ionic strength variations are virtually
separations are unnecessary and only simple solution eliminated. Reproducibility is good.
chemistry is required for p H adjustment and/or freeing To corroborate the quantitative recovery of fluoride b j
the fluoride ion from possible complexes. the bomb combustion method. an alkali fusion method (-7)
The occurrence of fluorine in British coals was the was used to decompose some of the coal samples. This
subject of an extensive investigation several years ago by method involves the ignition of coal mixed with an excess
Crossley (2-5) who developed a satisfactory method for of sodium carbonate at approximately 473 "C, followed by
fluoride determination. Finding that the existing methods fusion of the mixture at 1000 "C. In our study. the fused
contents were then extracted with hot water and the re-
(1) M S Frant and J W Ross, Jr , S o e n c e . 1 5 4 , 1 5 5 3 ( 1 9 6 6 ) .
(2) H. E. Crossley, J SOC. Chem Ind.. London. 63,280 (1944)
sultant solution was treated like that from the bomb ('om-
(3) H. E Crossley J SOC.Chem. I n d . . London. 63, 284 (1944) bustion method.
(4) H. E Crossley. J . SOC. Chem. l n d . London. 63, 289 (1944)
(5) H. E Crossley. J . SOC.Chem. I n d . . London. 63, 342 (1944) ( 6 ) Orion Research Inc Cambridge Mass Newsleffer 2. 2 (1970)

A N A L Y T I C A L C H E M I S T R Y , VOL. 46, N O . 9 , A U G U S T 1974 1321

 EXPERIMENTAL ture. The crucible and contents are heated in a furnace at about
475 “C for 24 hr. The crucible and contents are then heated over
Apparatus. A fluoride electrode and calomel reference elec- an air-boosted Meker burner (about 1000 “C) for 15 min to fuse
the mixture. The crucible contents then are extracted with hot
trode were used in conjunction with a Digital 112 Research pH
water. The pH is reduced to 5.0-5.2 (from -12) with 0.5M
meter (all from Corning Scientific Instruments, Medfield, Mass.).
HzS04. The solution is warmed in hot water to assist the removal
Plastic beakers and volumetric flasks were used in handling the
of COz. About 25 ml of the citrate ionic-strength-adjustment
fluoride-containing solutions. The contents were stirred with Tef- buffer are added to the solution. The total volume is built to a
lon-coated magnetic stirring bars. known value (generally to 250 m l ) . The potential is determined
A Parr oxygen combustion bomb containing the sample was
with the fluoride ion-selective electrode. Five milliliters of 0.01M
fired in standard coal calorimetry apparatus. A platinum crucible
standard fluoride solution are added and the potential is again
was used in the fusion experiments.
determined. The fluoride concentration is calculated from the
Reagents. All solutions were prepared with water that had known addition and from AE.
passed through a mixed anion-cation resin (Model MB-575 Illco-
Way Mixed-Bed Demineralizer, Illinois Water Treatment Co., RESULTS AND DISCUSSION
Rockford, Ill.). The water contained less than 0.01 ppm fluoride.
All reagents were reagent grade unless otherwise stated. The fluoride content of the coal samples was found to
Standard fluoride solutions were prepared as required from a range from 25 to 135 ppm, and to have a mean value of 60
1-liter stock solution containing 4.199 grams (1900 ppm, or 0.1M ppm. This is within the range of values reported by Cross-
F - ) ultrapure sodium fluoride (Alfa Inorganics, Inc., Ventron ley for British coals. Three of the coals were decomposed
Corp., Beverly. Mass.). The NaF had been dried at 120 “C. by both the bomb decomposition method and by alkali fu-
A concentrated citrate ionic-strength-adjustment buffer was
prepared by dissolving 294 grams sodium citrate dihydrate and sion. Fluoride results from both methods are shown in
20.2 grams potassium nitrate in 1 1. of water and adjusting the Table I. The agreement between the two decomposition
pH to 6.0 with citric acid. methods is satisfactory and serves to indicate that the
Primary standard benzoic acid was used to ensure complete major problems anticipated for the bomb combustion
coal combustion, and primary standard anhydrous sodium car- method-namely, the incomplete breakdown of the fluo-
bonate was used in the fusion experiments.
Five milliliters of 1M sodium hydroxide solution were used in
ride-containing component(s) in coal and the loss of fluo-
the bomb for each combustion, and 0.25M sulfuric acid solution ride during depressurization of the bomb-are not real-
was used for pH adjustment. ized.
An ultrapure grade of oxygen (Linde Division, Union Carbide As only about 1.0 to 1.5 grams of coal can be conve-
Corp.) was used for pressurizing the combustion bombs. niently burned to completion in an oxygen combustion
Samples. Fluoride analyses were carried out on more than 100 bomb, the concentration of fluoride in the 50-ml test solu-
coal samples, most of which were from the Illinois Basin. All of
tions is W 4to 10-5M. At this concentration level, the
the coal samples were either face-channel or drill-core samples
and were representative of the entire coal seam, although mineral major source of error in this method may arise from the
bands over three-eights of an inch thick were excluded. The coal pH a t which the initial potential is determined, as shown
samples were first crushed to pass a one-eighth inch screen; a by Butler (7) (Figure 1).At a pH above 7.0, hydroxyl ion
portion was then further comminuted to 20 mesh (‘740 pm) and interferes and a less positive potential is obtained a t 10-5M
then to 100 mesh (149 pm). At all stages of the sample prepara- fluoride concentration. With the known-addition method
tion, portions were subdivided by riffle sample splitters or by
quartering the sample. The final sample in each case, thus. was used here, the less positive initial potential reading leads to
representative of the original coal sample. In addition, fluoride higher fluoride results because AE is less than it should be
analysis was conducted on a sample blended at the National Bu- after the addition of the standard fluoride solution. In ad-
reau of Standards (Natl. Bur. Standards SRM 1631). This partic- dition, according to the Corning Information Bulletin El-
ular sample has been distributed to various laboratories for com- FL-2 concerning their fluoride electrode, the bicarbonate
parative trace element determinations and, hopefully, it will be- ion can also interfere if present at a concentration level
come a much needed “standard” coal sample. 1000 times greater than that of the fluoride ion. The re-
Procedure. Parr Bomb Combustion. One gram of coal ( < l o 0
mesh), weighed to the nearest 0.5 mg, is mixed with about 0.25 moval of the bicarbonate is therefore paramount.
gram benzoic acid in a fused quartz sample holder and placed in A t a pH less than about 5.0, hydrogen ions form well
a combustion bomb containing 5 ml 1M sodium hydroxide. If the known complexes, such as HFz-, with available fluoride
coal is ground sufficiently fine, the benzoic acid addition. which ions, thus producing low fluoride results.
assists combustion, is unnecessary. The bomb is pressurized with Table I1 shows comparative fluoride results for several
O2 to about 28 atmospheres and fired. At least 15 min are allowed
coal samples. The test solutions were buffered at pH 6.2
to elapse before the bomb is depressurized to permit the bomb to
cool and to condense the mists. The bomb is exhausted slowly and a t 7.2 with different citrate-citric acid ionic-strength-
over a period of about 1 min. Three approximately 5-ml aliquots adjustment buffers. Results also are shown for one sample
of demineralized water are used to rinse the bomb contents into a in unbuffered test solutions that had been adjusted mere-
50-ml plastic beaker. The beaker contents are stirred while the ly to a pH near 5.0 with 0.25M H2S04.
pH is adjusted to 5.0-5.2 with 0.25M HzS04. (Before adjustment, A t pH 7.2, the fluoride results are 10 to 22% higher than
the pH is generally about 7.0-7.5.) This reduces the initially high those determined at pH 6.2. In the unbuffered solutions
HCOs- content sufficiently to minimize its possible interference
in the fluoride determination. The beaker and contents are heat- with pH near 5.0, the fluoride results are much lower. In
ed in a hot water bath for about 10 min and then stirred again to addition to fluoride complexing with hydrogen ions in un-
drive off most of the dissolved COz. Five milliliters of the citrate buffered solutions, it is likely that considerable com-
ionic-strength-adjustment buffer are added to the beaker contents plexing also occurs with aluminum or silicon ions, which
to buffer the solution a t a p H of about 6.0, and to release most of are present from the breakdown of clays normally present
the fluoride from complexes with iron, aluminum, and hydrogen in coals. Edmond ( 8 ) has shown that the citrate buffer
ions. The beaker contents are then brought to room temperature.
The total volume is adjusted to 50 ml with demineralized water frees most of the fluoride from the latter complexes. As
and the potential is determined with the fluoride ion-selective was pointed out earlier, the known addition method does
electrode. One milliliter of 0.01M F - (190 ppm) is added to the not require complete freedom of the ion being determined.
beaker contents, and the potential is again determined. During In the unbuffered solutions at pH 5 , however, it would ap-
the determination, the contents are stirred moderately. The fluo- pear that in such dilute fluoride solutions, the fraction of
ride content in the coal is calculated from the AE resulting from
the known fluoride addition.
Alkali Fusion. In the alkali fusion method, 3 grams of coal ( 7 ) J N Butler Thermodynamic Studies Chap 5 in Ion-Selective
(weighed to the nearest milligram) are mixed with about 5 grams Electrodes R A Durst Ed Nat Bur Stand Spec Pub/ 314,
of anhydrous sodium carbonate in a platinum crucible. Approxi- Washington D C 1969
mately 2 grams more of the XaZC03 are used to cover the mix- ( 8 ) C R Edrnond Anal Chem 41, 1327 (1969)

1322 A N A L Y T I C A L C H E M I S T R Y , VOL. 46, NO. 9 , A U G U S T 1974

Table I. Results for Fluoride in Coals
Determined with the Ion-Selective Electrode

Coal
Fluoride, ppm

Bomb combustion Alkali fusion

i
NBS 1631 80 3: 4 (8 replicates) 86,88
C-14796 113,111,115 120,122
C-15456 103,100 100

Table 11. Results for Fluoride in Coals Determined

with Test Solutions at Different pH Values
Fluoride, ppm

Coal pH 7.2 pH 6.2 pH -5.0

PH
C-14796 123 113 ... Figure 1 . Effect of p H on the potential of a lanthanum fluoride
C-15448 118 98 ... electrode in sodium fluoride solutions of various concentrations.
C-15456 112 100 51, 45, 49
C-15038 79 68 ... The potential change with pH in the acidic region is caused by the forma-
C-16501 70 54 ... tion of H F 2 - , [From Butler (7)-reproduced with the author's permis-
C-14774 53 42 ... sion]

scribed by Gluskoter (10). The heavy mineral concen-

the fluoride that is free differs appreciably after the incre- trates, obtained by separating the low-temperature miner-
mental change in total fluoride concentration. al matter residue in bromoform, were examined with a
Crossley believed that fluorine in coal is present mainly scanning electron microscope (Cambridge Stereoscan)
as fluorapatite, CalOF2(P04)6. The occurrence of this that was equipped with an energy-dispersive X-ray spec-
phase in coal is also considered likely by Gluskoter et al. trometer. A distinct calcium phosphate mineral phase,
(9), who have described apatite petrifactions and nodules
presumed to be apatite, was clearly defined. It is the only
from Pennsylvanian shales in Illinois and have identified
Illinois coal examined in this fashion to date in which this
them as carbonate-fluorapatites. Some of these were in a
phase has been clearly discerned. Thus, for this particular
black fissile shale immediately overlying a coal seam.
sample, it would appear that the high fluoride values, to-
One of our coal samples appeared unique in that it had
gether with the poor reproducibility, result from the pres-
a fluoride content appreciably outside the range of the
ence of fluorine in relatively large discrete mineral frag-
other samples studied. Because the initial value of 265
ments that have densities greater than twice that of coal,
ppm fluoride appeared anomalously high, replicates were
with consequent nonuniform dispersement in the ground
run, and values of 153 and 240 ppm fluoride resulted. As
sample.
mentioned a t the beginning of this report, the heterogene-
ity of coal frequently makes it very difficult in trace ele- ACKNOWLEDGMENT
ment analysis to achieve satisfactory analytical reproduc-
The authors acknowledge with thanks the use of the
ibility. Some segregation of the inorganic fractions of
scanning electron microscope a t the Center for Electron
higher density within the ground coal samples quite possi-
bly can occur simply during sample handling. This was Microscopy, University of Illinois.
thought to be the likely explanation for the poor reproduc-
ibility with this particular sample. Unaltered mineral Received for review November 30, 1973. Accepted April 4,
matter residue was obtained from this coal by means of a 1974. This study was supported, in part, by the U.S.En-
radiofrequency, low-temperature ashing technique de- vironmental Protection Agency under Grant R800059 and
Contract 68-02-0246.
(9) H. J. Gluskoter, L H. Pierard, and H. W . Pfefferkorn. J . Sediment.
Petrol.. 40, 1363 (1970). (10) H. J. Gluskoter. Fuel. 44, 285 (1965)

Simultaneous Determination of Hafnium and Zirconium in

Silicate Rocks by Isotope Dilution
Lawrence B. Owen and Gunter Faure
Department of Geology and Mineralogy, The Ohio State University, Columbus, Ohio 432 10

The decay of naturally-occurring I7'jLu t o stable 176Hfis Previous work has shown that the uncommon rare-earth
of great interest to geologists because of its potential use in minerals gadolinite (FeYpBep(Si0s)z) and priorite (Y, Er,
determining the ages of Lu-bearing rocks and minerals. Ca, Fe, T h ) (Ti, NbI2O6) can be dated by the Lu-Hf meth-

A N A L Y T I C A L C H E M I S T R Y , V O L . 46, NO. 9, AUGUST 1974 1323