parently more severe chemical or physical interferences in
atomic emission spectrometry cannot be explained at pre-
sent. The addition of excess diverse ion appears to enhance
the production of free ground state molybdenum atoms; this
is shown by the increase of the atomic fluorescence and atomic
emission intensity in many instances. Similar results have
been reported in the atomic absorption spectrometry of molyb-
denum (6, 7).
lnterelement Interferences in Atomic Absorption
Analyses with the Nitrous Oxide-Acetylene Flame
J. Y. Marks and G . G . Welcher
Adoanced Materials Research & Deoelopment Laboratory, Pratt & Whitney Aircraft, Middletown, Conn.
The effects of flame and instrumental variables on
cation interference effects were evaluated. The
variables most critical in determining the magnitude
of cation interferences are the height of measure-
ment, fuel to oxidant ratio, and concentration of ana-
lyte in the salt matrix. With the proper selection of
operating parameters, many of the observed inter-
ferences were reduced. Possible interference mech-
anisms, such as lateral diffusion of analyte in the
flame and competition for oxygen were studied. It
was concluded that salt vaporization effects were the
most critical in determining interference effects. A
new, more pertinent method of expressing flame
conditions is presented. The new parameter ex-
presses the oxidant to fuel mole ratio as a fraction of
the stoichiometric ratio of 3 moles of nitrous oxide
to 1 mole of acetylene.
RECENT WORK in this laboratory on the development of atomic
absorption methods of analysis for major constituents in
nickel- ( I ) and cobalt-base ( 2 ) alloys has prompted a thorough
investigation into interelement effects. Confusion has arisen
from past reports of interferences in the literature. These
effects have been referred to as solute vaporization inter-
ferences, chemical interferences, and salt effects. These
interferences may be the result of either cation or anion con-
comitants. Anion effects are generally better understood and
in practice are easier to control than cation interferences;
therefore, only cation effects are considered in this study.
One method of decreasing cation effects is the long and tedious
preparation of standards to rigorously match the composition
of the sample. This necessitates knowing the composition
of the sample reasonably well before the analysis is performed.
Several mechanisms have been proposed to account for
interference phenomena. Alkemade (3) has attributed en-
hancement and depression effects to differences in volatility
of the matrix or compound in which the analyte atom is found
in the flame. An enhancement would result when the analyte
forms a more volatile compound or is dispersed in a more
volatile matrix. Conversely, depression of absorbance would
result from the formation of a less volatile compound or
matrix. It has been postulated that enhancements of certain
- (9) W. W. Harrison and W. H. Wadlin, ANAL.CHEM.,41, 374
(1) G. G. Welcher and 0. H. Kriege, At. Absorption Newslett., 8,
97 (1969).
(2) G. G. Welcher and 0. H. Kriege, unpublished data, 1970.
(3) C . Th. J. Alkemade, ANAL.CHEM.,38, 1252 (1966).
ANALYTICAL CHEMISTRY, VOL. 42, NO. 9, AUGUST 1970
ACKNOWLEDGMENT
We thank Dr. A. P. Rao for his assistance during the course
of this work, and Varian Techtron Pty. Ltd, Victoria, Aus-
tralia, for the provision of equipment and for the research
studentship awarded to one of us (R. W.).
RECEIVED
for review December 22, 1969. Accepted April 14,
1970.
oxide forming elements may be the result of a competition for
the available oxygen in the flame (4, 5). The atom popula-
tion is increased because of a decrease in the amount of oxi-
dized analyte in the flame.
Stupar and Dawson (6) have shown that a relationship
exists between the interelement effects and the size of the
particle remaining after evaporation of the solvent. In-
terelement effects may also be due to differences in the stabili-
ties of compounds formed in the flame (7,8). Several authors
have presented evidence that mixed oxides of the spinel type
may be responsible for interactions between some refractory
elements (9, IO). Koirtyohann and Pickett (11) have re-
ported recently a new type of interference in the nitrous oxide-
acetylene flame which may be the result of differences in the
rates of lateral diffusion of particles in the flame.
The major goal of the present study was the development of
generalized techniques for the suppression or elimination of
interelement interferences through a better understanding of
the atomization processes in the nitrous oxide-acetylene
flame.
EXPERIMENTAL
Apparatus. A Techtron Model AA-4 atomic absorption
spectrometer with a Techtron AB-50 grooved burner head
and a R106 photomultiplier tube was used for all absorbance
measurements. Standard hollow cathode lamps were used
as sources for atomic absorption measurements. Emission
measurements were made by inserting a Techtron type FE-4
beam chopper between the flame and the monochromator
entrance slit. The slit was 8 mm high and was variable
from 0 to 300 p wide. The beam from the hollow cathode
lamp was focused on the center of the flame and was 5 mm
.,
(4) S. Sachdev. J. W. Robinson. and P. W. West, Anal. Chim. Acta,
37, 12 (1967).
(5) T. Ramakrishna, P. West, and J. Robinson, ibid., 39, 81 (1967).
(6) J. Stuoar and J. B. Dawson. Aod. Oot., 7,1351 (1968).
i 7 j D. C: Manning and L. Capaiho-Delgado, Anal. Chim. Acta,
36, 312 (1966).
(8) M. D. Amos and J. B. Willis, Spectrochimica Acra, 22, 1325
(1966).
(1969).
(10) V. S. Sastri, C. L. Chakrabarti, and D. E. Willis, Talanta, 16,
1093 (1969).
(11) S. R. Koirtyohann and E. E. Pickett, ANAL.CHEM.,40, 2068
(1968).
1033
 ,250 - W
.240 -
Figure 1. Effect of varying nickel
concentration on absorbance of 100
ppm aluminum
0 2000 4000
in diameter. Because the beam was somewhat out of focus
at the extremes of the flame, the height of the flame sampled
was somewhat more than 5 mm.
Reagents. Solutions were prepared from chloride stock
solutions of the metals, where possible, in order to eliminate
any anion interferences. The vanadium stock solution was
0.8Nin sulfuric acid. Analyte was added to the test solutions
at the following levels: 100 ppm aluminum, 100 ppm titanium,
10 ppm chromium, and 40 ppm nickel. All test solutions
were made 1.2N in hydrochloric acid and contained 1000 ppm
potassium as potassium chloride. Distilled deionized water
was used in all dilutions.
Flame Variables. In normal operation nitrous oxide was
delivered from the tank via three stages of regulation to the
nebulizer at 11 psig. Acetylene was transported through
two stages of regulation to the burner at 0.2 psig. Except
where noted, the acetylene flow was adjusted to obtain a
“normal” atomic absorption flame with a red feather ex-
tending 7 mm above the primary reaction zone. Under these
conditions the nitrous oxide and acetylene flow rates were
5.6 l./min and 3.1 l./min, respectively, at 1 atm pressure and
0 “C.
The model AB-50 burner head features a raised slot of
width 0.53 mm and length 5.9 cm, resulting in an average
stream velocity at the burner port of 480 cmjsec. The height
of the red feather in analytically useful flames ranges from
1 to 15 mm, necessitating that at a constant nitrous oxide
flow of 5.6 l./min, the acetylene flow varies from 2.5 to 3.5
l./min. The combustion reaction under these conditions is
best written as (12):
3 NzO + CzHz --t 2 CO + 3 N2 + HzO
A stoichiometric flame results from an oxidant to fuel mole
ratio of 3 :1. The above reaction is favored over the reaction
normally written as:
5 NZ0 + CzHz + 2 COz + 10 N2 + H20
Carbon dioxide is almost completely dissociated at the tem-
perature of the nitrous oxide-acetylene flame, and maximum
temperature is predicted by a stoichiometry of three moles
of oxidant to one of fuel.
(12) J. G. Tschinkel, Pratt & Whitney Aircraft, private communi-
cation, 1969.
1034 ANALYTICAL CHEMISTRY, VOL. 42, NO. 9, AUGUST 1970
I 1 I I I I
6000 8000 10,ooo 12.000 14,000 16,ooo ia,ooo 20,000
PPM N I C K E L
The actual ratio of oxidant to fuel used in flame spectrometry
is less than the stoichiometric amount. Present practices
in reporting flame conditions are often confusing and mis-
leading. The oxidant to fuel mole ratio is of prime impor-
tance in defining the temperature of the flame and the flame
gas composition. Therefore it is suggested that the quantity
X (13), as well as total flow and red feather height, be used in
reporting flame conditions. The fraction X is obtained by
dividing the oxidant to fuel mole ratio by the stoichiometric
ratio of three, or:
moles oxidant/time
A =
moles fuel/time x 3
This fraction clearly expresses the oxidant to fuel ratio and its
relationship to stoichiometry. Analytically useful flames
involve oxidant to fuel ratios of approximately 2.2:1 to
1.6:1, or X = 0.73 to 0.53.
RESULTS AND DISCUSSION
Interelement Interferences. Detailed studies were made of
the interferences by several metals on the absorbances of
aluminum, titanium, chromium, and nickel. In each case,
the concentration of concomitant was varied while main-
taining the analyte concentration constant. The absorbance
of each analyte was measured at the height in the flame giving
optimum sensitivity.
Figure 1 shows the effect of varying amounts of nickel on
the absorbance of 100 ppm aluminum. It is typical of most
of the interferences studied in that at low nickel additions a
rapid change in absorbance is noted; as the nickel concentra-
tion is increased, the absorbance reaches a limiting value,
remains relatively constant, and at very high concentrations
begins to decrease gradually. The general shapes of inter-
ference curves are reproducible, but the exact concentrations
of concomitant at which inflection points occur generally
depend on the exact flame conditions used. Because of this
variability, care should be exercised when applying any re-
(13) A. G. Gaydon and H. G. Wolfhard, “Flames, Their Structure,
Radiation, and Temperature,” Chapman Hall, London, 1960,
p 34.
 Table I. Interferences on 100 ppm A1 Table 111. Interferences on 10 ppm Cr
Interfering Relative interference, % Interfering Relative interference,
metal Concomitant level, pprn metal Concomitant level. oom
50 200 5000 50 200 5000
Ti +8 +13 +I4 Ti
V
+32
+ 29
+33
+33 +38
+
36
V 0 +5 +21
Cr +I +7 +I4 Mn
Fe
-2
-6
+8
+1
++9
27
Mn +4 $5 +I1
Fe $4 +6 +15 co 0 +12 0
co
Ni
+3
-2
$5
0
++2610 Ni -4 +3 +25

Table IV. lnterferences on 40 ppm Ni

Table 11. Interferences on 100 ppm Ti
Interfering Relative interference,
Interfering Relative interference, metal Concomitant level, D u r n
metal Concomitant level, ppm
+5027 200 5000
A1
50
+12
200
+45
5000
+91
Ti +27 +
27
V - 20 - 26 - 38
V +8 +7 $7
Cr +19 +I9 +36
Mn 0 +2 - 29 Mn +l +lo +78
Fe 0 - 10 -42 Fe +5 +I1 +11
co $9 +I7 - 60 co +5 $7 +55
Ni - 19 - 25 - 65

ported interference data to a specific problem. In the tables
below, interference data are reported at three representative
concentration levels.
Interferences on Aluminum, Titanium, Chromium, and
Nickel. Tables I through IV show the effect of 50 ppm,
200 ppm, and 5000 ppm of various metal ions on the ab-
sorbances of aluminum, titanium, chromium, and nickel.
Absorbance measurements were made at the flame height of
maximum sensitivity for each analyte. Aluminum, chro-
mium, and nickel absorbances are enhanced in the presence of
metal concomitants, while titanium absorbance is suppressed
by most metals. It was found that the magnitude of the
effects shown in the tables was dependent upon flame and
instrumental variables. Therefore, a systematic study of
instrumental and flame variables was made.
Effect of Height of Observation on Interferences. The
effects of 200 ppm of various metal concomitants on 100 ppm
aluminum and 10 ppm chromium as a function of burner
height are shown in Figures 2 and 3, respectively. In gen-
eral, the magnitudes of the interferences vary with height in
the flame and are not necessarily maximum at the position
of maximum analyte absorbance. The magnitudes are
usually decreased at extreme heights in the flame.
Studies of absorbance as a function of height are especially
interesting in that they may also be viewed as studies of atom
population as a function of time and stoichiometry in the
flame. The typical nitrous oxide-acetylene flame has a rise
velocity of 700 cmlsec. Consequently the analyte spends
approximately 2 msec in the 15 mm of the flame normally
utilized for study.

Figure 2. Effect of height of ob-

servation on interferences on 100 ppm
aluminum
0 100pprnAl
0 100 ppm A1 + 200 ppm V
A 100 ppm A1 + 200 ppm Mn
100 pprn AI + 200 ppm Ti

01
0 I 1 I I I I I I I I
0 2 4 8 10 12 14 16 18 20

HEIGHT ABOVE BURNER (mm)

ANALYTICAL CHEMISTRY, VOL. 42, NO. 9, AUGUST 1970 1035

 '"[
,240

01 I I I I I I I I I I
0 2 4 6 8 10 12 14 16 18 20

HEIGHT ABOVE BURNER (mm)

Figure 3. Effect of height of observation on interferences on 10 ppm chromium

0 10ppmCr
0 10 ppm Cr + 200 ppm Ni
A 10 ppm Cr + 200 ppm Mn
Q 10 pprn Cr + 200 ppm Ti
a change in the pressure drop to the atmosphere causes a
Table V. Effect of Oxidant/Fuel Ratio change in gas flow rate and, therefore, a change in rise
on Interferences on 100 ppm A1 velocity in the flame. This changes the dwell time of the
Interfering Feather Relative interference, analyte and its matrix in any area of the flame. Second, a
metal height 1 mm 9 mm 16 mm change in pressure causes a slight change in solution uptake
X 0.73 0.57 0.53 rate since this is somewhat dependent upon the pressure drop
50 ppm Ti +13 +3 0 between the atmosphere and the end of the nebulizer capil-
200 ppm Ti +37 +4 -1 lary in contact with the nitrous oxide.
5000 ppm Ti +51 +6 -4
50 ppm Cr 0 0 -1 A study was made of the effect of changing nitrous oxide
200 ppm Cr $6 +4 +2 pressure on the interferences of titanium, cobalt, and chro-
5000 ppm Cr +8 +10 $1 mium on aluminum. The flow of acetylene was changed to
compensate for each change in nitrous oxide flow rate to
maintain a constant oxidant to fuel ratio. When the nitrous
Table VI. Effect of Oxidantpuel Ratio
on Interferences on 10 ppm Cr oxide pressure was varied from 12 to 18 psig, the relative
per cent interference changed very little, while the absolute
Interfering Feather Relative interference, %
absorbance of all the solutions increased by about 25%.
metal height 1 mm 9 mm 16 mm The fact that the interference changed very little with in-
X 0.73 0.57 0.53 creasing gas flow rate indicated that the residence time of the
50 ppm Mn 0 +2 0 salt particle in the flame was not significantly changed. The
200 ppm Mn -2 +I6
5000 ppm Mn
50 ppm Ti
0
0
++6+920 +33
+38
increased sensitivity is due to the improved nebulization of
the test solution.
200 ppm Ti
5000 ppm Ti
0
+8
++1610 +35
$46
Oxidant to Fuel Ratio. It was found that the nitrous oxide
to acetylene ratio could have an effect on the magnitude of
the interferences. Table V shows the effect of varying this
ratio on the interferences of titanium and chromium on
It should be pointed out that height studies yield only ap- aluminum. Table VI shows the results of a similar study
parent height profiles, since the height resolution of the in- of the interference of manganese and titanium on chromium.
strument is limited by the 8-mm slit height and the 5-mm di- The results are shown as a function of X and the height of red
ameter beam. At heights above the burner of less than 2.5 feather is indicated. The absorbance was measured a t the
mm, the photomultiplier is exposed to only a part of the beam, height of maximum sensitivity for the analyte alone a t each
as some light is eclipsed by the burner. The measured ab- of the three different fuel conditions. The ratio of nitrous
sorbance is the average absorbance throughout the area of the oxide to acetylene has a large effect on the magnitude of the
beam that passes through the slit. interferences. The interferences of titanium and chromium
Effect of Changing Nitrous Oxide Pressure. A change in on aluminum are reduced as the flame becomes more fuel-
nitrous oxide pressure produces two primary effects. First, rich, whereas the interferences of manganese and titanium

1036 a ANALYTICAL CHEMISTRY, VOL. 42, NO. 9, AUGUST 1970

 7mm
V E R Y FUEL RICH
,240- RED FEATHER

01 I I I I I I I I I
0 4 8 12 1G 20/0 4 8 12 16 20
HEIGHT ABOVE BURNER (niml

Figure 4. Effect of height of observation and oxidant to fuel ratio on enhancement of aluminum
by titanium
0 100 ppm AI, 7 mm feather
C 100 ppm AI +
500 ppm Ti, 7 mm feather
A 100 ppm AI, very fuel rich
Q 100 ppm A1 +
500 ppm Ti, very fuel rich

on chromium are increased with increasing fuel-richness.

Two factors reduce the interferences of titanium and chro-
mium on aluminum in a fuel-rich flame. First, the ab-
sorbance maximum of aluminum is shifted to a higher position
in the flame where vaporization is complete and salt vaporiza-
tion effects are eliminated. Second, the sensitivity is main-
tained at about the same level in the fuel-rich flame as that in
the normal flame. This is due to a maintenance of the atom
population by the increase concentration of reducing species
in the flame. These phenomena are shown more clearly in
Figure 4 where the absorbances of 100 ppm aluminum solu-
tions with and without 500 ppm titanium are plotted as a
function of height in the flame at two different fuel to oxidant
ratios. At a point 15 mm above the burner in a fuel-rich
flame, titanium interference is essentially eliminated with only
a 25z decrease in sensitivity. It is interesting to note that
in both a normal flame and a fuel-rich flame the position
of maximum aluminum absorbance is shifted approximately
1 mm lower in the flame in the presence of titanium. This
effect was not observed in any other case.
The increased magnitude of interferences on chromium
with the reducing flame is harder to understand. In this case
the position of maximum absorbance does not vary with the
reducing nature of the flame and all data were taken with
center of the beam 7 mm above the burner. The sensitivity
for chromium is reduced somewhat in a fuel-rich flame and
there is a slight decrease in flame temperature, but these
factors alone would not account for the large increase in inter-
ference.
Effect of Organic Solvents. Acetone was selected as a rep-
resentative solvent and the effect of various amounts of ace-
tone on the interference of chromium on aluminum is shown
in Table VII. The measurements were made in the region
of the flame having maximum aluminum absorbance with
Table VII. Effect of Acetone on
Interference of Cr on 100 ppm AI
Acetone concn, Relative interference,
VOl. z 100 ppm Cr 5000 pprn Cr
0 +lo
5 +6 +5
25 +3 +8
50 +3 +3
no acetone present, Acetone has little effect on the magni-
tude of the interference, although it does increase the sensi-
tivity for aluminum.
Effect of Solution Flow Rate. The effect of solution as-
piration rate on interferences was evaluated by substituting
a Techtron Model D4-21V continuously variable nebulizer
for the constant flow model used for previous measurements,
and varying the solution flow rate while holding all other
parameters constant. Solution flow rates were measured
at each setting of the adjustable nebulizer. The absorbance
values were then measured at a height 5 mm above the
burner. The effect of rate of solution aspiration on the
interferences of titanium on aluminum, manganese on chro-
mium, and nickel on titanium was studied. The magnitude of
the interference is reduced slightly at lower flow rates but is
not eliminated. Stupar and Dawson (6) have discussed the
relation between solution flow and interference effects and
concluded that high flow rates produced large salt particles in
the flame which were more difficult to vaporize.
Effect of Matrix Dilution. If interferences are affected
by changes in composition of the salt matrix left after evap-
oration of the solvent, then the addition of a large amount
of an inert salt should significantly reduce the difference in

ANALYTICAL CHEMISTRY, VOL. 42, NO. 9, AUGUST 1970 e 1037

 Table V I E Effect of Matrix Dilution
on Interferences on 100 ppm AI
Relative interference,
Interfering metal No Dilution 10,000 ppm KCI
50 ppm Ni -2 +1

-
-aE'
l3

12

11
t
-
200 ppm Ni
5000 ppm Ni
50 ppm Cr
200 ppm Cr
5000 ppm Cr
+1
+7
0
26 +
+I4
+4
+6
+2
0
0
- 50 ppm Ti +8 +2
y 10 200 ppm Ti +13 +3
K
2
W
9 -
5000 pprn Ti +14 -1
>
8a Table IX. Effect of Matrix Dilution
on Interferences on 10 ppm Cr
Relative interference,
No 10,000 10,000

:t Interfering metal
50 ppm Mn
200 ppm Mn
4000 pprn Mn
dilution
-2
+8
NDa
ppm K
-3
-3
+
14
ppm AI
-2
ND
0

5000 pprn Mn
50 ppm Ni
+ 27
-4
ND
+2
-3
0
200 ppm Ni -2 0
5000 pprn Ni
50 ppm Fe
+-6+253 +- 1 514 0
ND
200 ppm Fe +1 - 19 ND
6 5 4 3 2 1 0 1 2 3 4 5 6 5000 ppm Fe 4-9 +18 ND
HORIZONTAL DISTANCE FROM C E N T E R OF SLOT ( m m )
a Not determined.

Figure 5. Distribution of atomic aluminum in flame

Absorbance
0 0.160 LJ 0.040
c 0.100 0 0.030
0 0.080 0 0.020
A 0.060 0.010
atomization between solutions containing analyte only and
those containing both analyte and concomitants. To test
this assumption, the effects of varying amounts of nickel,
chromium, and titanium on aluminum were studied in the
presence of 10,000 ppm potassium (added as the chloride).
Results are shown in Table VI11 and indicate a significant re-
duction in interferences on aluminum. A similar study was
made on interferences on chromium. Both potassium chlo-
ride and aluminum chloride were used in this study as matrix
diluents at the 10,000 ppm level of metal (added as the chlo-
ride). As can be seen from Table IX, the interference effects
of manganese and nickel on chromium are reduced with
potassium chloride additions and practically eliminated with
aluminum chloride. The interference of iron on chromium is
actually increased upon addition of potassium chloride.
Matrix dilution with aluminum chloride was studied for the
interferences of nickel and cobalt on titanium, and manganese
and titanium on nickel, with only limited success.
The fact that analytical results are not always seriously
affected by interelement interferences is probably due to a
matrix dilution effect. Most determinations are carried out
in the presence of a major constituent which acts to dilute
the salt matrix left after evaporation of the solvent.
Laterial Diffusion of Analyte in Flame. Koirtyohann and
Pickett (11) have suggested that some enhancement effects
are due to a decrease in lateral diffusion in the flame with in-
creased particle weight. To test whether a similar mechanism
might be responsible in some part for the enhancement ef-
fects seen in our work, two solutions were prepared, one con-
taining aluminum and the other containing aluminum and
5000 ppm chromium. The aluminum absorbance was then
measured in both solutions as a function of lateral translation
in the flame at different heights. A series of figures have been
prepared in which positions in the flame of equal absorbance,
thus equal atomic concentration, were connected by a line.
Figure 5 shows the result of this study for aluminum in the
absence of chromium. This figure also shows the dimensions
of the beam and monochromator slit. If the diffusion mech-
anism is valid for this case, the aluminum absorbance, in the
presence of chromium, should be increased in the center of
the flame and decreased in the outer portions. A plot of the
absorbance data obtained using the solution containing both
chromium and aluminum did show an enhancement in the
center of the flame when compared to the data in Figure 5 ,
but there was no decrease in absorbance in the outer portions
of the flame. Consequently, we conclude that a decrease in
lateral diffusion is not responsible for the observed enhance-
ment.
Competition for Oxygen. It was suggested (4, 5) that a
competition for oxygen might be responsible for enhance-
ment effects noted between strong oxide-forming elements.
Some of the strongest monoxides and their reported dissocia-
tion energies are given below.
Oxide Do kcal/mole
Ti0 166
vo 148
A10 137
These data suggest that the enhancement effect of titanium on
aluminum represents one of the most favorable cases for
competition for oxygen. Both metals form very stable oxides,
but the dissociation energy of titanium monoxide is 21x
higher than that of aluminum monoxide and would be ex-
pected to successfully compete with aluminum for oxygen.

1038 ANALYTICAL CHEMISTRY, VOL. 42, NO. 9, AUGUST 1970

 0.400 -

Y
y0.m -
Figure 6. Interference of 1000 ppm $
titanium on 1000 ppm aluminum a
0 1OOOppm A1 9
1000 ppm A1 + 1000 ppm Ti
0.200 -

0 1 2
HEIGHT ABOVE BURNER (mm)

Two solutions were prepared, one containing 1000 ppm to lower the likelihood of aluminum oxidation. In the
aluminum and the other 1000 ppm aluminum and 1000 ppm second case, titanium or a titanium species would reduce
titanium. Both solutions were made 1.2N in hydrochloric oxidized aluminum. Both processes seem unlikely when
acid. To confirm that the enhancement effect of titanium on considered in the light of other flame species present. When
aluminum was still evident at the 1000-ppm aluminum level, a solution which is 1000 ppm in titanium is aspirated into the
absorbance profiles were made of the aluminum solution and flame, its concentration in the flame, expressed as the mole
the solution containing both aluminum and titanium. As fraction is approximately 2 X 10-5. This represents a solu-
seen in Figure 6, the interference is still present at the 1000 tion flow rate of 5 . 5 ml/min and assumes that 10% of the solu-
ppm concentration of aluminum. A competition for oxygen tion reaches the flame. Considering the very low concentra-
between titanium and aluminum might act in two ways to tion of titanium in the flame and the fact that other more
increase the amount of atomic aluminum as shown below: highly reducing species such as atomic and molecular hy-
(1) Ti + 0 Ti0-+ drogen, cyanogen, and carbon are available for reduction, it
t would seem unlikely that titanium plays a major role in the
(atomic or any titanium species) reduction of aluminum oxide.
i To test these assumptions three solutions were prepared,
(2) Ti + NO Ti0
-+ +A1° one of which contained 1000 ppm aluminum, another 1000
In the first case titanium would reduce the concentration of ppm aluminum and 1000 ppm titanium, and the third 1000
oxygen or oxidizing species in the flame to such an extent as ppm titanium. All solutions were made 1.2N in hydro-

Figure 7. Mutual effects of aluminum and - I-

titanium on the emission intensity of their Iwn

c
monoxides I
w
A . T i 0 emission 2
0 1OOOppmTi I-

0 1000 ppm Ti + 1000 ppm A1 5w

B. A I 0 emission a
A 100OppmAl
0 1000 ppm A1 + 1000 ppm Ti

12 16 20
HEIGHT A B O V E BURNER

ANALYTICAL CHEMISTRY, VOL. 47 NO. 9, AUGUST 1970 0 1039

chloric acid. The emission intensity of aluminum monoxide
at 4867 A was then measured as a function of height in the
flame, both in the solution containing aluminum and in the
solution containing aluminum and titanium. The aluminum
monoxide emission intensity was corrected for background
from the hydrochloric acid and the considerable emission from
titanium at the aluminum monoxide bandhead. In a similar
manner the emission intensity of titanium monoxide was
measured at 5004 A in the solution containing only titanium
and in the solution containing both titanium and aluminum.
The results of this study are shown in Figure 7. The titanium
monoxide emission remains unaltered by the presence of
aluminum. However, the aluminum monoxide emission
intensity does show a definite decrease in the presence of tita-
nium at heights between 0 and 12 rnm above the burner. It
can be concluded that competition for oxygen may account
for some of the enhancement effects observed between re-
fractory elements. The competition probably occurs in the
solid or liquid phase before salt evaporation is complete.
In this state the effective concentration of both concomitant
and analyte would be greatly increased, thus increasing the
likelihood of reaction.
CONCLUSIONS
These studies suggest the complexity of cation interference
effects. The magnitude, and in some cases the direction of
interferences, is dependent upon a variety of experimental
Flame Emission Method for Determining Heats of
Combustion of Selected Compounds
J. J. Kroeten,’ H. W. Moody, and M. L. Parsons2
Department of Chemistry, Arizona State University, Tempe, Arizona 85281
A new method for determining heats of combustion of
organic compounds was found using flame emission
spectroscopy. Solutions of alcohols, carboxylic acids,
and amines in methanol were introduced into an en-
trained air-hydrogen or oxy-hydrogen flame. The
most intense CH emission bandhead at 431.5 nm was
measured and a computer was used to correlate the
data. A linear response for emission intensity vs.
the heat of combustion was found for compounds in a
homologous series. The slopes were the same for
compounds containing the same functional group.
The slopes for solutions containing different functional
groups were quite different. When comparing the
experimental values to the literature values, an av-
erage agreement of 3.6% was found. The standard
deviations of the data were obtained from the calcu-
lated curves and found to be 3.3, 23.3, and 48.3 kcal
for the amines, alcohols, and acids, respectively.
The time required to complete the entire procedure
i s about 1 hour.
BASICALLY, there are only two general techniques for deter-
mining the heat of combustion of organic molecules-theo-
retical calculations and experimental calorimetric methods.
The theoretical approaches include the concept of correlating
the displacement of valence electrons to the heat of combus-
Present address Syntex Corp., Pharmaceutical Analytical De-
partment, Stanford Industrial Park, Palo Alto, Calif.
To whom all correspondence should be addressed.
1040 ANALYTICAL CHEMISTRY, VOL. 42, NO. 9, AUGUST 1970
variables, which probably account for many of the dis-
crepancies in interference studies reported in the literature.
When constant flame conditions are used, the most probable
explanation for the interferences reported in this study is
the difference in volatility of the analyte when accompanied
by other metal species, most concomitants increasing the
volatility of the analyte. It is important to note that the
volatility of the matrix in terms of boiling point and heat of
vaporization is not necessarily of prime importance, but that
the volatility of analyte is in some manner increased or de-
creased in the presence of concomitants. The evaporation
rate of small salt particles in the flame is a complex function
of many factors including drop size, diffusion coefficient of the
evaporating species, surface tension, and heat transfer char-
acteristics. Many interferences can be reduced or eliminated
by the proper selection of flame conditions and salt concentra-
tion. A more descriptive study of atomization processes is
the subject of a later paper.
ACKNOWLEDGMENT
The authors thank J. G . Tschinkel for the many helpful
discussions and suggestions. The authors also thank 0. H.
Kriege for his critical reading of this manuscript.
RECEIVED
for review March 26, 1970. Accepted May 18,
1970.
tion (2) and the use of additivity rules (2). Some of the calori-
metric approaches are the use of rotating bomb calorimeters
(3), bomb calorimeters (4, and flame calorimeters (5). The
precision of these techniques is usually around 0.5 to 1.5 %.
These methods have several disadvantages, such as the need
for expensive equipment, the length of time needed to obtain
suitable results, e . g . , some take 24 hours or longer (3), and the
inability to distinguish between some geometrical isomers (2).
The flame spectroscopy method described in this paper
appears to be a fast and simple way of determining heats of
combustion. The technique described here is empirical;
however, there is a physical basis for the phenomenon. It is
known that the emission intensity from atoms and molecules,
e.g., the CH molecule, produced from the combustion of
species in the hot flame gases is directly proportional to the
number of these molecules existing per unit volume of hot
(1) S. Morris, Kharasch, and Ben Sher, J. Phys. Chem., 29, 625-
658 (1925).
(2) S. W. Benson and J. H. Buss, J. Chem. Phys., 29, 546-572
(1958).
(3) W. D. Good, D. W. Scott, and G. Waddington, J. Phys. Chem.,
60, 1080-89 (1956).
(4) F. D. Rossini and E. J. Prosen, J. Res. Nut. Bur. Stand., 33,
255 (1944).
(5) G. Pilcher, H. A. Skinner, A. S . Pell, and A. E. Pope, Trans.
Faraday SOC.,59, 316330 (1963).