312 ANALYTICA CHIMICA ACTA

DISSOCIA’I’ION AND IONI%ATION EFFECTS IN

ATOMIC Al3SORPTION SI’ECTROCHEMICAL ANALYSIS

D. C. MANNING AND l,Uls C~\t~~~CIiO-l~I~l,GADO

Pcrftiu-Elmer Corporufion. NorwrtUc, Coma. (U.S.A.)
(Rcccivctl March rsth, 1@3)

One of the fundamental differences between flame emission spectroscopy and

flame atomic absorption spectroscopy is that in the former the signal derives from
excited atoms, while in the latter the signal derives from unexcited or ground-state
atoms. Atomic excitation is strongly dependent on flame tempcraturc, and thercfore
relatively small variations in flame temperature c;msc large variations in the flame-
emitted signal. On the other hancl, the number of ground-state atoms present is much
less dependent on flame tcmpcraturci. If one could assume that the excitation
phenomena were the only ones that must be considcrcd, for all practical purposes the
number of atoms in .the grouncl state, and therefore the absorption signal, would be
independent of flame temperature. Rut this is not the case. In flarnc spectroscopy as
commonly practised, in orcler for an atom to be free, either in the excited or unexcited
state, it is necessary that the solvent ancl sample be vaporized, ancl the sample be
clissociatccl to free atoms. The complctcncss of this process depencls, among other
things, on the flame tcmpcrature, the element species present (anion as well as cation),
and the concentrations of the elements in the original solution. Thcsc variables have
been studied primarily in connection with flame emission spectroscopy” but the con-
clusions apply equally well to flame atomic absorption spectroscopy, since the forma-
tion of free atoms is required in either case.
In the early work with flame atomic absorption, two observations were made
that vcrificd similar cxpericnce in flame emission spectroscopy. Firstly, it was noted
that solutions of some elements provided no absorption signal when introduced into
the flames then commonly used (air with propane, city gas, hydrogen, or acetylene).
Secondly, it was noted that the absorption signal procluced by a given concentration
of certain elements variccl, depending on the presence of certain other anions and/or
cations. It is fairly well established that the first effect is due to the inability of the
flame to clissociatc the compounds of those elements not providing absorption signals,
and that the second effect is due to different rates of vaporization and dissociation,
depending upon the energy recluired to break apart the particular compounds formed,
which in turn depends upon the species present. Early efforts in flame emission
spectroscopy to use hotter flames to increase the clissociation were largely unsuccessful
until. it was realised that it was also necessary to provide a reducing atmosphere
(fuel-rich condition) to inhibit oxide and/or hydroxide formation”-“. Using a hotter
flame (-3000~) under reducing conditions, various workers have shown that at least

Anal. Chirn. rfcfn, 36 (1966) 312-318

DISSOCIATION AND IONIZATION IN ATOMIC ABSORPTION 313

partial vaporization and dissociation of the compounds of most if not all metals can be
achieved. The hotter flame Calsogreatly reduces or eliminates the effect of vaporization
and dissociation with respect to different anion or cation species present5a. Therefore,
if the number of free ground-state atoms were a function only of vaporization and
dissociation, it would bc logical to use the hottest possible flame that is convenient to
obtain.
However, there is another factor to consider which is also temperature-de-
pendent: ionization. When one or more electrons are removed from an atom, the ion
does not absorb radiation at the same wavelengths which it absorbs as a neutral atom.
In an analytical procedure, if one is measuring the radiation absorbed by ground-state
atoms, and a certain fraction of these is ionized, the measurement will differ from the
condition of no ionization by this amount. If the ionization is not suppressed, or some
other compensation is not made, an error will be introduced.
For any given element concentration in solution when aspirated into a flame,
thcrc is a corresponding partial pressure of the clement in the gas phase. For a given
partial pressure the ionization increnscs with temperature. Figure I shows this
relationship for calcium at two partial pressures. The data for thisgraph wcrc taken from
GAYDON AND WOLFHAIUJ~. who made the calculations using the SAHA equation”. At

PER CENT IONl2AlION COWCENTRATION OF ADDED POTASSIUY AND/OR PHOSPHOWJS. IPPUI

Fig. I. The incrcnsc of calcium ionization with tcmpcmturc, calculated for two partial prcssurcs.
Tcrnpcraturc of an air-acctylcnc flnmc is about 255o’JC; tldilt of a nitrous oxide-ncctylcnc kmc
is about 3200’K.
Big. 2. The cffcct of zdkxl potassium chloritlc and/or phosphoric acid on the absorption signal of
2 p.p.111. CdCiUm iLt 4227 If.

low calcium concentrations and high flame temperatures the ionization is significant.
Therefore, we have two requirements (among others) that are contradictory : a
flame hot enough to provide adequate volatilization and dissociation, and a flame
cool enough to prevent unacceptably large ionization. Fortunately there is a reason-
ably simple solution to this seeming dilemma, which has been used in emission flame
spectroscopy. If one adds a relatively large amount of an easily ionized metal such
as one of the alkalis to the sample solution, the electron density in the flame is greatly
increased when the solution is atomized. The additional electrons suppress the ioni-
zation of the metal of interest, to a level that no longer produces a significant error.
It is therefore possible to work with a hot, fuel-rich flame to provide sufficient vapor-
ization and dissociation, and to add a relatively large amount of an easily ionized

And. C/rim. Acta, 36 (1966) 312-318

314 D. C. MANNING, L. CAPACHO-DELGADO

metal when it is necessary to inhibit the ionization of the element to be determined.

Figure z illustrates the effects which have been described. Various amounts of
potassium as KCl, phosphorus as HsPOd, and a combination of these two were added
to a solution of z rug of calcium (as the chloride) per ml. Absorption values were ob-
tained with an air-acetylene flame and a nitrous oxide-acetylene flame at the calcium
4227 A atom resonance line. In the air-acctylenc flame there is negli~ble effect from
the added potassium chloride, confirming the calculation (Fig. I, -2600°K) of the
SAHA equation. The presence of phosphoric acid depresses the signal markedly, as the
result of the formation of stable calcium phosphate. This effect has been studied in
detail by a number of workers *2.6$0.When both potassium chloride and phosphoric
acid arc acldcd, the effect is essentially the same as with phosphoric acid alone, in-
dicating that in this cast the potassium chloride has little effect on vaporization and
dissociation.
The data from the nitrous oxide-acctylcne flame show that calcium sensitivity
without adclcd ions is about twice that of the air-acetylene flame. The addition of
potassium into this flame evidently causes an increase in the calcium atom population.
The natural conclusion is that the increase is clue to suppression of ionization. It is
possible that the potassium also increases the rate of dissociation”, which would
produce the same effect, However, since it does not increase the dissociation in the
lower-temperature air-acetylene flame, as is shown by the curve, it is more likely that
the cntirc cnhanccment is due to calcium-ion suppression rather than more efficient
vaporization and dissociation.
The absorption enhancement of calcium by phosphoric acid in the nitrous
oxide flame is very small compared to that caused by potassium chloride, and is
apparently due to an increase in the rate of dissociation, since the absorption of
calcium measured at the 3934 A ion resonance line is unaffected by phosphoric acid,
up to 5000 p,p.m. When both phosphorus and potassium were added, the effect was
almost identical to that obtained with potassium alone. It is interesting to note that,
when calcium is determined in the prcscncc of large amounts of phosphorus and potas-
sium the nitrous oxide-acetylene flame is IO times more sensitive than the air-acety-
lene flame.

-.-_._- .a
060
0.60 ,’
8’
----. NtO-CIH1 FLAME #’ ,’
,’ 0.50 .’
- AIR-Cati FLAME l’ ,’
,’ .’
,’
w 0.40 .-2iw&n____,_ &f
lu *.
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,/’
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fg 0.30 **. ,’
4’
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a’ = 0.20 %_
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________------ l.
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3 (

CONCENlAAllON OF ADDED POTASSIUM OR PHOSPHORUS, (PPYI CONCENTRATION OF ADDED POTASSIUY. (PPU)

Fig. 3. The cffcct of added potassium chloride or phosphoric acid on 50 p.p.m. barium absorption
at 5.535 A.
Fig. 4. The cffcct of added potassium chloride on the absorption of barium at the atom and ion
lines in the nitrous oxide-acetylcno flame.

Awal. Chinr. Acta, 36 (1966) 312-318

l.>ISSOCIATION AND IONIZATION IN ATOMIC ABSORPTION 315

Figure 3 summarizes similar data taken with barium. The effect of potassium
chloride and of phosphoric acid is negligible in the air-acetylene flame. In the nitrous
oxide-acetylene flame there islittle or no enhancement on addition of phosphoric acid,
and a striking enhancement from added potassium chloride. The effect is the same as
was seen for calcium; the difference is in degree. The addition of potassium chloride
markedly reduces the barium ion concentration as shown by the data in Fig. 4, in
which the absorbance of the atom line and the ion line are plotted on the same scale.
This is very similar to results observed with strontium in earlier worklo. This Figure
illustrates the increase in sensitivity one can obtain by using the high-temperature
flame to achieve improved vaporization and dissociation, along with a large addition
of an easily ionized metal to inhibit ionization.

Calcitlntion of the degree of ionization

For those elements such as calcium and barium having a sensitive ion resonance
line located within the wavelength region 2000-So00 A, it is possible to calculate the
de&Tee of ionization in a hot flame using absorption readings taken with and without
added potassium chloricle. Absorption readings are taken at both atom and ion
resonance lines. In setting up the calculation, at least two assumptions are made. First,
it is assumed that the addition of potassium chloride to the flame does not change the
total number of free atoms and ions of the element present in the flame; that is, the
degree of vaporization and dissociation is not materially changed. The second assurnp-
tion is that the Beer-Lambert relationship holds over the absorbance range used for
the calculation. To establish this, it is not sufficient to construct a typical absorbance
VS. concentration curve using plain salt solutions with the nitrous oxide-acetylene
flame. It is a well established fact s.7.” that the percentage of atoms ionized varies
inversely with their concentration in the flame.
To reduce the possible effect of more efficient vaporization and dissociation,
one should use as small an amount of potassium chloride as possible that gives a
measurable change in ionization. This also reduces any error due to deviation from the
Beer-Lambcrt law, since differences in absorbance produced are less with a small
amount of added potassium. The validity of the assumptions can be tested by repeat-
ing the experiment using larger concentrations of added potassium chloride.
Two equations can be written involving the absorbance readings obtained

TABLE t
ABSORBANCX FROM FREE ATOMS AND IONS”
______-.________ ..__. __.____- -__- --.--- - -- -

GCewienl Concrr. A lsorburrce

(WW) 0 p.+n. I< +x0 p.p.nr. Ii +300 p.p.m. I< $- 5000 p.Q.nr. Ii

Uarium 5.2 cv
55356 Ba I 50 0.052 0.079 (X.52) 0.409 (7.87) 0.620 (x1.9)
4554.0 Ba I1 50 0. ‘109 0.387 (0.947) 0.199 (0.487) 0.037 (0.090)

Calcium G.1 cv
4226.7 Ca I 2 0. I99 0.221 (1.11) 0.297 (1.48) ~:~~~ I’ j63)
3933.7 Ca II 2 0.050 0.040 (0.800) 0,004 (0.088) 0

a Numbers in pirrcnthcscs arc ratios of absorbance with addctl potassium to rtbsorbanccwithout

added potassium.

Anal. Cl&n. Acta, 36 (rgG6) 312-318

 3x6 D. C. MANNING, L. CAPACHO-DELGADO

from the free atoms and ions in each of 2 solutions of a given element concentration,
one solution also containing potassium as the chloride. In Table I are listed the ab-
sorbance readings obtained for solutions of barium and of calcium taken at the most
sensitive atom and ion line of each. Potassium as the chloride was added in the
amounts: o, IO, 300, 5000 p.p.m. The numbers in parentheses are the ratios of ab-
sorbance with addccl potassium to no added potassium. Let us use barium as an
example. If x equals the fraction of free ground-state neutral atoms, and y equals the
fraction of free ground-state neutral ions present in the flame when measuring the
absorbance of the barium solution without potassium, WC can form 2 independent
equations involving x and y for each concentration of potassium. Using the barium
values with IO p.p.m, potassium added:
x+y =I

x.fjz x+0.947 y = I

Solving for x and y, we obtain:

N = 0.092; 3’ = 0.908

Therefore, the barium in the plain solution with the nitrous oxide-acetylene flame is
gr “/;‘,ionized.
Treating the calcium results similarly, with IO p.p.m. potassium added we
obtain :
zc = 0.644; y = 0.356
The calcium in the solution containing no potassium is 36% ionized.
These results can be compared with values calculated using the SAHA equation*,
which may be written in the form:

+ 2,5 log ‘f + log ZL+- log 110- 6.18

where -7:= fraction of the atoms that are ionized, P=total pressure in atmospheres of
the clcctrons and the metal in all forms in the burnt gases, T=absolute flame temper-
ature, Y=ionization potential of the element, ,zt+=partition function of the ion,
11o=partition function of the atom.
To evaluate the fraction of atoms ionized (x) we can use establishedl* values
of v, and calculated values” for ,i~+and 210.
zl+ 210
Calcium ;I.,, 2.0 I.0
l3arium 5.21 2.9 1.3
The absorption measurements of atoms and ions are taken in the nitrous oxide-
acetylene flame in the reaction zone close to the burner top. While chemical and
thermal equilibrium may not be established in this region2 for purposes of calculation
we can assume a temperature that has been measured for a nitrous oxide-acetylene
flame in cquilibriuml”, which is 3230%. Also it is reasonable to assume a pressure
P of 10-0 atmosphercs?*l3. Using these values in the SAHA equation, we obtain the
numbers given in Table II compared to those derived from the experiment. This is the
calculated ionization of the calcium and the barium in solution with no added
potassium.

Anal. CJtinr. Acta, 36 (rg6G) 312-318

DISSOCIATION AND IONIZATION IE: ATOMIC ABSORI’TIOS 3x7

TABLE IL
APPAl<ENT IONIZATION (%)
-.-------_ _. .._--.-__- _-- -. -... -.-----
Culciwu BUYilW
---_---.--_--

Observed
with IO p.p.m. I< 35.6 go.8
with 300 pp.m. I< 3-W 93.3
with 5000 p.p.m. IC 38.G w-3

Calctrlded
From !%\llA 4r.9 90.5
__ . ._ _ .__ . _ _. _._ .__.,.. _ ..___ _.__ _________.______

If the addition of potassium chloride did appreciably incrcasc the vaporization

and dissociation, the apparent ionization values calculated from the absorbances of
atoms and ions would incrc,ase with an increase in added potassium. The difference
between the values for various concentrations of potassium shown in Table II appears
to be random, indicating that if there is a change in dissociation, it causes an error
which is less than other contributing effects.

SU hIMAR\

Use of a nitrous oxide-acetylene flame in atomic absorption spcctrophotometry

reduces or eliminates certain chemical interferences that have been observed in cooler
flames. However, ionization increases with temperature, and is significant for some
elements in the nitrous oxide-acetylene flame. Ionization can be reduced by adding an
easily ionized metal (e.g. alkali metal) to the solution. Elements likely to be determined
using the nitrous oxide-acct_vlene flame which will be significantly ionized are:
Al, 13a, Ti, V, %r, Hf, Nb, SC, Y, the lanthanidcs and the actinidcs. The ionization of
an element in the nitrous oxide-acetylene flame can be readily calculated by taking
absorption readings, provided that relatively sensitive atom and ion resonance lines
are available. This technique possibly could be used to establish ionization potentials
or partition functions of those lanthanide elements that are not now well known.

L’emploi d’une flamme oxyde nitreux-acetylene en spectrophotomdtric par

absorption atomique diminue ou elimine certaincs interferences chimiques observecs
dans des flammes plus froides. Cepcndant, l’ionisation augmente avec la temperature
et est importante pour certains elements (Al, Ba, Ti, V, Zr, Hf, Nb, SC, Y, lanthanides
et actinides). Elle peut &r-e. Gduitc par addition d’un metal facilement ionise (ex.
metal alcalin) B la solution. 11 cst possible de ddterminer les potcntiels d’ionisation
encore ma1 connus de lanthanides.

ZUSAhIhfENFASSUNG

Die Verwendung einer Distickstoffoxid-Acetylen-Flamme bei der Flammen-

absorptionsspektroskopie reduziert oder eliminiert gewisse chemische Storungen, die
in kalteren Flammen beobachtet wurden. Die mit der Temperatur steigende Ionisa-

AnaC. Ckinr. Acta. 36 (x966) 3X2-318

318 D. C. MANNING, L. CAPACHO-DELGADO

tion ist jedoch becleutsam fur einigc Elemente in dieser Flamme. Die Ionisation kann
durch Zugabe tines leicht ionisierenden Metalls (z.B. Alkalimetall) zur Losung
reduziert wcrden. Folgcnde Elemente, wclche wesentlich ionisiert werden, lassen sich
gut unter Verwendung dieser Flamme bestimmen: Al, Ba, Ti, V, Zr, Hf, Nb, SC, %?,die
Lanthaniden und die Aktinidcn. Die Ionisation eines Elements in der Distickstoff-
oxid-Acetylen-Flammc kann schnell mittels der Absorption berechnet werden, wenn
dafiir gesorgt wird, class relativ empfindliche Atom- und Ionenresonanzlinien ver-
fiigbar sind. Mit dieser Technik k&men moglichcrweise noch nicht gut bekannte
Ionisationspotentiale oder Verteilungsfunktionen von den Lanthanidelementen fest-
gestellt werden,

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AtaaZ. Cl&x. /lclu, 36 (1966) 312-318