f, Reproducibility.
Total iron concentrations were gener-
'
Std. 0-5 pA
FeQH) : ;
a
; ;
BCR-1 I
µ
A
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-0:35 -015 ^0*05
Volt
vs Ag/AgCI
Figure 4. AC polarograms for a standard ([Fe(lll)]
and a USGS Rock Standard
rate of (100 ± 1)% was found. With ferrous ion, as shown in
Figure 2, a very small ferric contribution was sometimes
observed, and a recovery rate of (99 ± 1.5)% was found for
this species.
Standard Rocks. Table I shows data obtained on five
standard rocks, along with average values obtained via
other methods (21) and the range of values reported in the
literature (22). The polarographic results lie well within
the range of published data and generally within ±2% of
the average values compiled from all available data.
Figure 3 shows typical dc polarograms of three of the
samples, and Figure 4 gives ac polarograms of a standard
solution and a sample.
Considering that the ferrous, ferric, and total iron were
all obtained from the one experimental approach, com-
pared with other methods where two or even three experi-
ments are required, the ease and convenience of the pro-
posed method can be appreciated.
Relative Photoelectron Signal Intensities Obtained with
Magnesium X-Ray Source
Hervé Berthou and Christian K, Jdrgensen
Département de Chimle minérale et analytique, Université de Genéve, 1211 Geneva 4, Switzerland
X-Ray photoelectron spectroscopy has often been used for
quantitative (or semiquantitative) analysis of metallic or al-
loyed samples. Since people use either an aluminum or a
magnesium X-ray source, the relative photoelectron signal
Intensities of 76 elements are compared for both sources.
Differences arise though the same intensity behavior Is ob-
served. Further on, the relative reproducibility is much bet-
ter with a high-intensity magnesium source (10 to 15%)
482 · ANALYTICAL CHEMISTRY, VOL. 47, NO. 3, MARCH 1975
ally reproducible to ±1.5% or better. The reproducibility of
ferrous and ferric concentrations obviously depends on the
concentration ratio of two species. However, in these sam-
ples where the ratio lies within the range 1:3 to 3:1, better
than ±3% could be obtained.
Limitations. The greatest limitation to the present
method is that it is applicable only to samples amenable to
the reported dissolution procedure. Thus refractory mate-
rials, such as chromite, would not be suitable. In principle,
any sample for which the standard dichromate titration (1,
2) procedure can be used to determine the ferrous content,
can be subjected to the polarographic method to provide
information on the ferrous, ferric, and total iron content.
The additional information gained and the advantages of
the instrumental method of analysis can therefore be ap-
preciated. Data for the USGS Standard Rocks only are re-
ported in this paper to validate the method. However, pres-
ently, work on a wide array of other samples has been com-
menced or is contemplated, and it is certainly applicable to
a considerable number of determinations.
LITERATURE CITED
= 1.00 X 10~3M) (1) L. Shapiro and W. Brannock, U.S. Geol. Surv. Bull. 1144A, A48 (1962).
(2) L. C. Peck, U.S. Geol. Surv. Bull., 1170 89 (1964).
(3) L. E. Reicker and J. J. Fahey, U.S. Geol. Surv. Bull., 1144 B (1962).
(4) J. L. Bouvier, J. G. Sen. Gupta, and S. Abbey, Geol. Surv. Can., Paper
72-31 (1972).
(5) J. J. Llngane, J. Amer. Chem. Soc., 68, 2448 (1946).
(6) L. Meites, Anal. Chem., 20, 895 (1948).
(7) M. Pinta, “Detection and Determination of Traces Elements," Israel Pro-
gram for Scientific Translations, Jerusalem, 1966, pp 434-437.
(8) L. Cernatescu, R. Ralea, G. Burlacu, M. Furnlca, O. Bot, and M. Radu,
Bull. Stiintif, Sect, Stiln. Tech. Chim., 6, 185 (1954).
(9) I. M. Issa, R. N. Issa, and I. F. Hewaidy, Chemist-Analyst, 47, 88 (1958).
(10) G. L. Bien and E. D. Goldberg, Anal. Chem., 28, 97 (1956).
(11) B. Rehak, Hutn. Listy, 5, 432 (1957).
(12) E. P. Parry and D. P. Anderson, Anal. Chem., 45, 458 (1973).
(13) A. M. Bond, Anal. Chem., 45, 2026 (1973).
(14) A. M. Bond, V. Biskupsky, and D. A. Wark, Anal. Chem., 46, 1551
(1974).
(15) S. C. ¿reason and D. E. Smith, Anal. Chem., 45, 2401 (1973).
(16) F. Van Der Pol, M. Sluyters-Rehback, and J. H. Sluyters, J. Electroanal.
Chem., 45, 277 (1973).
(17) D. E. Glover and D. E. Smith, Anal. Chem., 44, 1140 (1972).
(18) D. E. Glover and D. E. Smith, Anal. Chem., 45, 1869 (1973).
(19) A. M. Bond and J. R. Thackeray, Chem. Instrum., 4, 299 (1972).
(20) K. Yamashita and H. Imai, Bull. Chem. Soc. Jap., 41, 1339 (1968).
(21) F. J. Flanagan, Geochim. Cosmochim. Acta, 37, 1189 (1973).
(22) F. J. Flanagan, Geochim. Cosmochim. Acta, 33, 81 (1969).
Received for review August 2, 1974. Accepted September
20,1974.
a
than with aluminum (20 to 30%). The intensity variation
cannot be straightforwardly correlated with the 233-eV dif-
ference between the photon energies 1486.6 and 1253.6
eV. In a few cases, a kind of sharing due to secondary pro-
cesses such as shake-up or multiplet splitting might explain
the discrepancies from the values expected using the ratios
of theoretical photoionization cross-sections.
Table I. Relative Photoelectron Signal Intensities Obtained with a Magnesium X-Ray Source for Elements from
Lithium to Arsenic (Values Previously Obtained with an Aluminum X-Ray Source Are in Parentheses)
Ele-
ment Is 2s 2p 3s 3p 3d

Li 0.03
(0.02)
Be 0.09
(0.07)
C 0.25 0.009
(0.27)
N 0.4 0.013
(0.4)
O 0.6 0.03 0.015
(0.6) (0.02) (0.01)
F 1.0 0,045 0.021
(1.0) (0.04) (0.02)
Na 2.0 ± 15% 0.24 0. 14
(2.0) (0.13) (0.08)
Mg 0.19 ± 15% 0.14 ± 15%
(3) (0.15) (0.10)
A1 0.20 0.22
(0. 22) (0.18)
Si 0. 36 0. 52
P 0,23 0.43
(0.3)
s 0.46 0.05 0.07
(0.35)
Cl 0. 28 0.54 0.04 0.04
(0.25) (0.42) (0.04) (0,05)
K 0. 5 1.0 0.10 0.21
(0.9) (0.08) (0.12)
Ca 1.35 0.08 0.20
(0.8) (0.06) (0.12)
Sc 1. 5 0.23
Ti 1.2 0. 17
(0.9) (0.11)
V 1.4 ± 20% 0.16 ± 20%
(0.9) (0.11)
Cr 1.3 ± 40% 0. 2 ± 40%
(1.1) (0.18)
Mn 1.15 0.3 0.09
(1.0) (0.15) (0.03)
Fe 1. 15 0.32 0.08
(1.8) (0.25) (0.06)
Co 0.09 1.2 0.25 0.5 0.09
(2.1) (0.07) (0. 28) (0.1)
Ni 1.15 0.23 0.56 0.26
(1.7) (0.37) (0.08)
cud) 1.9 0.25 0.62 ± 20% 0.46 ± 20%
(3.0) (0.4) (0.15)
Cu(n) 1.9 0.7 0.33
(1.5) (0.3) (0.12)
Zn 2.2 0.4 0. 57 ± 40% 0.4 ± 40%
(3.2) (0.25)
Ga 2. 1 0.45 0.6 0.6
(4) (0.45) (0.4)
Ge 0.2 0.3 0.3
(4) (0.4) (0.4)
As 0.33 0.45
(3) (0.38) (0.48)

X-ray photoelectron spectroscopy has generally been
used for studing chemical bonding and the chemical influ-
ence of ligands on a central atom (1, 2). However, one as-
pect of this technique has often been underestimated—
namely, its capability to give quantitative (or at least, semi-
quantitative) results. C. D. Wagner has been the first (3) to
demonstrate that X-ray photoelectron spectroscopy can be
a method for quantitative analysis. Nowadays, people turn
their attention on such results in view of application in me-
tallic surface studies (4, 5) complex chemistry (6), in catal-
ysis (7), or in adsorption of alkaline metals on phosphates
(8). On the other hand, theoretical calculations of pho-

ANALYTICAL CHEMISTRY, VOL. 47, NO. 3, MARCH 1975 · 483

Table II. Intensity Ratios between the Relative Intensities Obtained with Magnesium and Aluminum X-Ray Sources
for the Same Elemental Shell (Photoionization Cross-Section Ratios for 1253.6- and 1486.6-eV Photons,
Calculated from Nefedov et al. (9), Are Given in Parentheses)
Element Is 2s 2p 3s 3p 3d

Li 1.5 (1.72)
Be 1.3 (1.67)
C 0.93 (1.63)
N 1.0 (1.61)
O 1.0 (1.59) 1.5 (1.56) 1.5 (1.84)
F 1.0 (1.57) 1.1 (1.55) 1.1 (1.82)
Na 1.0 (1.53) 1.85 1.51) 1.75 (1.79)
Mg 1.3 (1.48) 1.4 (1.77)
Al 0.91 (1.47) 1.22 (1.75)
P 1.43 (1.71)
s 1.33 (1.7)
Cl 1.38 (1.69) 1.0 (1.43) 0.8 (1.67)
K 1.11 (1.66) 1.25 (1.42) 1.75 (1.63)
Ca 1.69 (1.65) 1.33 (1.41) 1.67 (1.61)
Ti 1.33 1.54
V 1.56 1.45
Cr 1.18 1.11
Mn 1.15 2.0 3.0
Fe 0.64 1.28 1.42
Co 0.57 3.57 1.78 0.92
Ni 0.68 1.51 3.25
cud) 0.63 1.55 3.06
Cu(H) 1.27 2.33 2.75
Zn 0.69 1.6
Ga 0.52 1.33 1.5
0.75 0.75
As 0.88 0.94

toionization cross-sections for 1486.6- and 1253.6-eV pho-
tons have recently been published and compared with ex-
perimental results for elements with Z 3 to 92 (9-11).
=
= w for this unit of intensity. In practice, we established a set of
secondary standards such as nitrogen Is, oxygen Is, sulfur 2p3/2 or
chlorine 2pa/2. When a large number of compounds with or without

fluorine are compared, a consistent set (within 10 to 15% reproduc-

Independently of Wagner, we also measured the photo-
electron signal intensities in hundreds of stoichiometric
compounds (containing 77 elements) which we analyzed
with an aluminum source (1) and resuméd in a subsequent
paper (12). Our results agreed well with those of Wagner.
As we now use a magnesium X-ray source, such intensity
measurements were repeated and we found differences.
The most striking example arises with the Cs3dg/2 signal
decreasing to about half its previous value. On the other
ibility) of intensities can be established. Actually, the reproducibil-
ity mentioned above is better than the 20 to 30% previously ob-
tained with the aluminum X-ray source. This fact might be corre-
lated to the much higher electronic density around the samples
when bombarded with 1253.6-eV photons coming from the high in-
tensity source. When metallic or alloyed samples are analyzed, the
reproducibility becomes better than 2%. Relative intensities given
in Tables I-V refer to photoelectron signals with j =
l + when
resolved. The intensity ratio (l + l)/l between the signals for j = l
+ % (at lower ionization energy) and j =
l -

V2 is generally re-

hand, 4f photoelectron signal relative intensities are en-
hanced, such as for hafnium 4f7/2 by about 60% (13). Com-
parison will be made with theoretical results.
EXPERIMENTAL
Our measurements are made with a Varían IEE-15 photoelec-
tron spectrometer. A retarding potential is applied to the samples
to keep the energy of emitted photoelectrons entering the analyzer
constant at 36 eV. A high intensity magnesium X-ray source is run
at 11000 V and 0.15 A. With these standard settings, the resolution
(defined as the presence of two distinct maxima in the superposi-
tion of two Gaussian signals with the same one-sided half-width
and same height, occurring (1) for a distance above 1.70 of the
two component maxima) is close to 1 eV and the value of 2 is 1.3
eV and 1.2 eV for metallic gold 4f7/2 and for metallic silver 3ds/2,
respectively. Each region up to ten was scanned one after the
other, whereas a small intensity decrease may be observed during
spected. Nevertheless, this latter rule is not observed for elements
such as calcium, scandium, titanium, and vanadium where the
2ps/2 signal is much higher by about three times than the 2pi/2 (for
which the full width is only marginally broader than the 2p3/2),
and for heavy elements when the 4p level is considered. For mea-
suring photoelectron signals, we only consider the signal height at
maximum in pulses per second and then, normalized it by compar-
ison with the reference signal height(s) of known intensity. If we
were to consider the area under the curves, equivalent to the
height at maximum multiplied by the full width, the disagreement
previously observed for the 2p and 4p levels is less pronounced but
still exists. For analytical purposes, the area is far less suitable be-
cause of the mildly undulating background. Finally, the results
given through Tables I-V are reproducible within 10% (unless
quoted).
Figures 1 and 2 resumé the relative intensities given as a func-
tion of the atomic number Z for the Is, 2s, 2p3/2, 3s, 3ds/2, 4s, 4p3/2,
4ds/2, 4f7/2, 5p3/2 and 5d shells of elements with Z 3 to 92.
=

measurements, because of hydrocarbon contamination. We cir-
cumvented this problem by scanning the regions sequentially—i.e.,
a few scans per region repeated 25, 50, or 100 times. Powdered
samples are generally stuck onto an one-sided Scotch tape (600P,
No. 15, 3M Company) consisting of polymerized CH2 groups. Pro-
Whereas results given by W. J. Carter et al. (11) predict a smooth
exponentially-like increase for Is, 2s, 2p, 3d, 4d, and 4f shells with
the atomic number, our results show variations and something like
steps in a staircase for 2p, 3d, and 4f shells while increasing dra-
matically with Z. Discontinuities in intensity appear between Z =

grams are run between 60 to 100 minutes. 17 and 20 for 2p and 3p shells (less pronounced in the latter case)
As done previously, we determined the relative intensities of the and between Z = 28 and 31 (also true for 3s and 3d shells). Later
strongest signals of a given element in comparison with the fluo- on, discontinuities also appear between 37 and 39 and between 47
rine Is signal. In the following, we use the colloquial name wagner and 50 for the 3d and 3p shells. Generally, discontinuities ap-

484 · ANALYTICAL CHEMISTRY, VOL. 47, NO. 3, MARCH 1975

Figure 1. Relative intensities of 1s, 2s, 2p, 3s, 3p, 3d, and 4p photoelectron signals as a function of the atomic number Z (the left-hand higher
scale refers to the 1s, 2p, and 3d relative intensities)

Table III. Relative Photoelectron Signal Intensities Obtained with a Magnesium X-Ray Source for Elements from
Selenium to Barium (Values Previously Obtained with an Aluminum X-Ray Source Are in Parentheses)
Elem ent 3s 3p 3d 4s 4p 4d 5p

Se 0.31 0.5
(0.5) (0.5)
Br 0.2 0.5 0.6 0.11
(0.5) (0.55) (0.08)
Rb 0.2 0.6 0.66 0.18 ± 25%
(0.7) (0.6) (0.10)
Sr 0.75 1.72 ± 30% 0.23
(0.8) (0.8) (0.2)
Y 1.05 ± 20% 1.3 ± 20% 0.55 ± 50%
(0.85) (0.9) (0.2)
Zr 0.6 1.5 0.18
(0.8) (1.2) (0.2)
Nb 0.55 1.35 ± 30% 0.10 ± 40%
(0.8) (1.2) (0.2)
Mo 0.6 1.6 0.18 0.1?
Ru 0.07 0.47 2.0 0.065 0.21 0.16
(0.8) (1.8) (0.14)
Rh 0.075 0.4 1.9 0.04 0.16 0.2 ± 50%
(1.1) (2.1) (0.2) (0.2)
Pd 0.05 0.5 2.15 0.05 0.085 0.28 ± 25%
(0.6) (1.9) (0.1) (0.2)
Ag 0.03 0.4 2.45 0.04 0.09 0.3 ± 20%
(0.8) (2.5) (0.1) (0.35)
Cd 0.05 0.6 3.35 0.055 0.095 , 0.63 ± 25%
(1.0) (3.0) (0.1) (0.5)
In 0.75 4.5 ± 15% 0.095 0.95 ± 15%
(4.0) (0.7)
Sn 0.1 0.88 3.95 ± 25% 0.15 0.9 ± 45%
(5.0) (0.8)
Sb 0.65 5.35 0.115 0.135 1.1 ± 25%
(6.0) (1.0)
Te 0.43 4.5 ±35% 0.115 0.09 0.93 ± 50%
(4.0) (0.7)
I 0.31 3.9 0.75 ± 20% 0.06
(4.0) (0.6) (0.05)
Cs 4.05 0.65 0.71 0.10
(6.5) (1.3)
Ba 3.9 1.1 ± 15% 0.14 ± 20%
(5.5) (1.3) (0.15)

ANALYTICAL CHEMISTRY, VOL. 47, NO. 3, MARCH 1975 · 485

Table IV. Relative Photoelectron Signal Intensities Obtained with a Magnesium X-Ray Source for the Lanthanides
(Values Previously Obtained with an Aluminum X-Ray Source Are in Parentheses)
Element 3d 4d 4f 5P

La 3.35 ± 25% 1.33 ± 40% . .

(2) (1.0)
Ce 2.4 ± 15% 0.65 ± 20% 0.11 0.25 ± 20%
(2) (0.5) (0.1)
Pr 1.8 ± 25%. 0.71 ± 25% 0.09 0.23 ± 35%
(2) (0.4) (0.07)
Nd 2.2 ± 20% 0.73 ± 20% 0.18 0.17
(3) (0.5) (0.06)
Sm 2.2 0.62 ± 15% 0.29 ±30% 0.22
(2.3) (0.15)
Eu 2.2 0.85 0.35 0.21
(2.2) (0.2) (0.15)
Gd " 0.98 0.48 0.24 ± 15%
(3)' (0.8) (0.3) (0.1)
Tb 0.83 0.57 0.33
Dy 0.46 ± 40% 0.24 0.22
(0.4) (0.2) (0.07)
Ho 0.72 0.34 0.31
(0.25) (0.25)
Er 0.99 ± 30% 0.58 0.34
(0.5) (0.3) (0.15)
Tm 0.95 0.75 0.17
(0.4) (0.35)
Yb 0.7 ± 25% 0.97 0.28 ± 35%
(0.6) (0.5) (0.25)
Lu 1.3 2.34 ± 30%· (?) 0.45 ± 25%
(0.5) (0.75)

Table V. Relative Photoelectron Signal Intensities Obtained with a Magnesium X-Ray Source for Elements from
Hafnium to Uranium (Values Previously Obtained with an Aluminum X-Ray Source Are in Parentheses)
Element 4p 4d 4£ 5s 5P Sd 6p

Hf 0.85 1.45
(0.8) (0.9)
Ta 0.71 1.7
(1.0) (1.4)
W 0.6 1.7
Re 0.3 0.6 2.1 ± 15% 0.2 0.12
(0.8) (1.8)
Os 0.25 0.8 2.65 0.23 0.17
(0.3) (1.0) (1.3) (0.3)
Ir 0.25 0.85 2.6 0.2 0.20
(0.5) (1.2) (1.8) (0.25)
Pt 0.2 0.6 2.5 0.26 0.15 0.25
(0.3) (0.9) (1.8) (0.4)
Au 0.25 0.65 2.5 0.07 0.21
(0.35) (0.9) (2.2) (0.05) (0.3)
Hg 0.3 0.6 2.5 0.22
(0.8) (2.4) (0.25)
T1 0.25 0.63 ± 40% 3.1 0.1 0.1 0.48
(1.0) (2.5) (0.4)
Pb 0.55 3.9 ± 20% 0.45 ± 20%
(0.9) (3.2) (0.5)
Bi 0.72 ± 20% 4,3 ± 30% 0.55
(1.0) (3.5) (0.5)
Th 0.84 ± 30% 6.8 ± 30% 0.9 ± 25% 0.23
(1.2) (7) (1.0)
U 0.7 ± 30% 3.1 0.41 0.05
(1.3) (7) (0.9) U5f 0.11

486 · ANALYTICAL CHEMISTRY, VOL. 47, NO. 3, MARCH 1975


z when using magnesium. Whereas we noticed two maxima
Figure 2. Relative Intensities of 4d, 4f, 5p, and 5d photoelectron sig-
nals as a function of the atomic number Z (the right-hand higher
scale refers to the 4f relative intensities)
pearing in different shells are seen roughly within the same gaps.
On the other hand, 2s, 3s, 3p, 4s, 4p, 4d, and 5p intensities seem to
scatter around a mean value instead of increasing smoothly with Z
as predicted. For these last shells, it is noted that their intensities
are quite low.
RESULTS AND DISCUSSION
Elements from Lithium to Arsenic. The relative inten-
sities of photoelectron signals obtained with a magnesium
X-ray source are resumed for elements from Z = 3 to 33 in
Table I and compared with those obtained with aluminum
(quoted in parentheses through Tables). Whereas Is and 2s
signal intensities are roughly equivalent for both sources,
the 2p intensities show an increase from carbon to chromi-
um and a decrease for the subsequent elements. On the
other hand, they remain almost constant for manganese,
iron, cobalt, and nickel, and again increase from copper to
gallium, while for aluminum photons the increase was the
general trend. This step appearing from manganese to
nickel might be explained by a kind of intensity sharing be-
cause, for these elements, the 2p signals are accompanied
by satellite structure due to shake-up or shake-off process
(14, 15) or to multiplet splitting (interelectronic repulsion)
(1) when the ground state has positive total spin quantum
number S. As also shown in Table I, the 3s, 3p, and 3d sig-
nal intensities are generally enhanced when using magne-
sium instead of aluminum photons, but their variations fol-
low the same trend in both cases.
Theorists concentrate interest on the Is signal increasing
strongly from Z = 3 to 11 as a function of Z, 0.002(Z l)3 —
w. They argue that the intensities are proportional to the
X-ray absorption cross-section (9, 10). For s and p elec-
trons, it can be approximated by the absorption edge going
as (—3rd) power of the photon energy (as suggested by Kra-
mers (12)) whereas higher l- values correspond to delayed
maxima above 100-eV photon energy. Quite generally, the
transition elements show intensities 2 to 10 times lower
than expected from interpolation between the surrounding
elements or by extrapolation.
As seen from data given by Nefedov et al. (9), the ratios
between the total photoionization cross-sections for 1253.6-
and 1486.6-eV photon energies decrease slowly from lithi-
um to calcium for the Is, 2s, 2p, and 3p shells and vary
from about 1.7 to 1.4. Hence, we could expect a much larger
difference between relative intensities with both sources.
However, this predicted increase does not agree well with
our experimental results, as seen in Table II (figures in pa-
rentheses refer to Nefedov data). The increase is much less
ANALYTICAL CHEMISTRY, VOL. 47, NO. 3, MARCH 1975
with the exception of calcium where the agreement is good
enough.
It is noted that the magnesium X-ray source does not
make so much difference between copper(I) and copper(II)
2p signals as aluminum, but this difference appears to a
larger extent for the 3p and 3d shells.
Elements from Selenium to Barium. Table III gives
the relative intensities of the 3s, 3p, 3d, 4s, 4p, 4d, and 5p
shells for elements from Z = 34 to 56. On the whole, there
is not so much change when using aluminum or magnesium
for these shells, with the exception of the last seven ele-
ments. In general, when considering s shells, their intensi-
ties are very low and their maximum lies around 0.1 w.
As mentioned above, the most surprising difference ap-
pears with the cesium 3ds/2 intensity decreasing by 40%
for antimony 3ds/2 and cesium 3ds/2 with a minimum for
tellurium and iodine, the second has disappeared to give
one maximum followed by several elements (Te, I, Cs, Ba)
of almost similar intensities. This behavior also appears for
the 4d shell.
Elements from Lanthanum to Lutetium. The relative
intensities of the 3d, 4d, 4f, and 5p shells of the lanthanides
are resuméd in Table IV. In this table, figures giving poor
accuracy are quoted. The reason is that we find a big dis-
crepancy when comparing the intensities measured for
fluorides and oxides. Actually, a factor of two generally ap-
pears between both species. We attempted to explain this
anomalous behavior by the fact that lanthanide oxides
might be quite sensitive to water vapor by forming on the
surface (the photoelectrons leave from the first 30 Á) hy-
droxides of the type M(OH>3 instead of M2O3. So far, fig-
ures given in Table IV take into account such formation
and, hence, are the average results of fluorides, hydroxides
(?), and complexes such as NaX2MCle where X is Cs, Rb,
or Tl. Nevertheless, 3d shell intensities are roughly equiva-
lent, with the exception of lanthanum. In this series, the
largest differences appear in the 4d, 4f, and 5p shell inten-
sities which are well enhanced when using a magnesium
source.
Elements from Hafnium to Uranium. Table V re-
sumés the relative intensities of the 4p, 4d, 4f, 5s, 5p, 5d,
and 6p shells of elements from Z = 72 to 92. While the 4p
or 5d shell intensities remain almost constant from rhen-
ium to thallium and the 4d shell intensities are decreased
when using a magnesium source, the 4f signals as men-
tioned beforehand are well enhanced and stay almost con-
stant from osmium to mercury. The last two elements show
a quite different behavior when using a magnesium source.
Whereas the thorium 4f and 5d shell intensities are quite
comparable to those obtained with an aluminum source,
the uranium 4d, 4f, and 5d shells decrease by 46, 56, and
54%, respectively, when considering the results obtained
with magnesium. This rapid jump from thorium to urani-
um is not at all understood since there is only 233-eV dif-
ference between both photon energies (this is also true for
cesium 3d). One may expect that the satellite structure ob-
served in certain uranium compounds (1) contributes to
this anomalous low intensity.
CONCLUSION
Our results are to some extent offered for comparison
with other models of photoelectron spectrometers, since it
is not evident that our intensities relative to fluorine Is do
not contain specific properties of the Varían IEE-15 appa-
ratus. Nevertheless, the few results given in literature (4,
11) suggest that roughly the same relative intensities
would be obtained in general, with the probable exception
· 487
of very high ionization energies (just below the photon en-
ergy) where the discrimination from small escape width of
electrons having low kinetic energy also introduces a seri-
ous problem of vertical sample inhomogeneity.
LITERATURE CITED
(1) C. K. Jorgensen and H. Berthou, Mat. Fys. Medd. Danske Vid. Selskab,
38, No. 15 (1972).
(2) K. Siegbahn, C. Nordling, G. Johansson, J. Hedman, P. F. hieden, K.
Flamrin, U. Gelius, T. Bergmark, L. O. Werme, R. Manne, and Y. Baer,
"ESCA Applied to Free Molecules," North-Holland Publishing Company,
Amsterdam, 1969.
(3) C. D. Wagner, Anal. Chem., 44, 1050 (1972).
(4) P. E. Larson, Anal. Chem., 44, 1678 (1972).
(5) R. M. Friedman, J. Hudls, M. L. Perlman, and R. E. Watson, Phys. Rev. B
8, 2433 (1973).
(6) L. E. Cox and D. M. Hercules, J. Electron Spectrosc., 1, 193 (1973).
(7) R. M. Friedman, R. I. Declerk-Grimee, and J. J. Fripiat, Proc. Int. Conf.
Electron Spectrosc. Namur (1974), in press.
Determination of Nanogram Quantities of Carbonyl Compounds
Using Twin Cell Potential Sweep Voltammetry
Badar K. Afghan, Achut V. Kulkarni,1 and James F. Ryan
Analytical Methods Research Section, Canada Centre for Inland Waters, P.O. Box 5050, Burlington, Ontario, Canada L7R 4A6
Twin cell potential sweep voltammetry is used to determine
and differentiate various classes of carbonyl compounds in
natural waters and industrial effluents. A systematic study
of polarographlc behavior of these compounds in various
media, such as alkaline medium, citrate buffer, and in the
presence of various amines, is reported. It is possible to de-
tect and distinguish various classes of carbonyl compounds
using the above media. Individual carbonyl compounds can
also be determined down to 0.25 ¿¿g/liter without any sepa-
ration or preconcentration of the sample. The above method
is applied to determine various carbonyl compounds in natu-
ral waters and industrial effluents.
The determination of “carbonyl compounds” in natural
waters and industrial effluents is of considerable interest
(1). In this paper, the term “carbonyl compounds” is used
in a collective sense to describe those aldehydes and ke-
tones which are known for their strong taste, odor, corro-
sive and related problems.
In our laboratory a preliminary survey of various sam-
ples ranging from drinking waters to industrial effluents
was carried out to obtain information concerning the na-
ture and levels of these compounds. This survey indicates
that formaldehyde and related compounds do occur in con-
siderable quantities in some pharmaceutical, chemical, pe-
troleum, and industrial effluents. Levels as high as 50 mg/
liter, in terms of formaldehyde equivalent concentrations,
are found in some industrial waters (2).
Although the methods used in our preliminary investiga-
tions give reasonably accurate results for relatively clean
waters, they are not suitable for industrial effluents and re-
ceiving waters (2). The fluorometric procedure was too spe-
cific for formaldehyde alone, and the colorimetric method
1
Permanent address, Analytical Chemistry Division, Bhabha
Atomic Research Centre, Trombay, Bombay, 400085, India.
488 · ANALYTICAL CHEMISTRY, VOL. 47, NO. 3, MARCH 1975
(8) C. K. Jprgensen, L. Balsenc, and H. Berthou, Chimia, 27, 384 (1973).
(9) V. I. Nefedov, N. P. Sergushin, J. M. Band, and . B. Trzhaskovskaya, J.
Electron Spectrosc., 2, 383 (1973), (for 7 = 1 to 20).
(10) J. J. Huang and F. O. Ellison, Chem. Phys. Lett., 25, 43 (1974), (for 7 =
1 to 10).
(11) W. J. Carter, G. K. Schweitzer, and T. A. Carlson, Proc. Inte. Conf. Elec-
tron Spectrosc., Namur (1974), in press (for 7 = 3 to 92).
(12) C. K. Jorgensen and H. Berthou, Chem. Soc. Faraday Discuss., 54, 269
(1973).
(13) C. D. Wagner, private communication.
(14) C. S. Fadley, Chem. Phys. Lett., 25, 225 (1974).
(15) T. A. Carlson, J. C. Carver, L. J. Saethre, F. Garcia Santibanez, and G.
A. Vernon, Proc. Int. Conf. Electron Spectrosc., Namur (1974) in press.
RECEIVED for review July 1, 1974. Accepted October 3,
1974. Grant (2-323-70) from the Swiss National Science
Foundation permitted the purchase of the photoelectron
instrument.
gave very high molar extinction coefficients for the un-
known compounds present in these effluents. Although the
colorimetric procedure was relatively more reactive to car-
bonyl compounds, it did not react with most common al-
dehydes such as benzaldehyde, vanillin, furfural, etc.
Therefore, work was initiated to develop a method which
would react with as many commonly occurring carbonyl
compounds as possible and which would more accurately
determine the total carbonyl content of all samples.
The majority of carbonyl compounds condense with a
wide variety of amines to produce >C=N- compounds
and water (3). Resultant products such as imines, substi-
tuted hydrazone, oximes, and semicarbazones are also
known to reduce at the dropping mercury electrodes (4, 5).
Furthermore, these addition products reduce at a dropping
mercury electrode (DME) involving the same number of
electrons regardless of the nature of the carbonyl com-
pounds (6-8). Similar values for the diffusion current con-
stants (I) for some aldehydes with semicarbazide have al-
ready been reported (9). Therefore, it should be possible to
obtain the same order of current for similar concentrations
for different carbonyl compounds and, hence, use this ap-
proach for the determination of total carbonyl content in a
sample.
The use of semicarbazone for the determination of car-
bonyl compounds has been reported in the literature (9,
10); however, earlier workers used conventional dc polarog-
raphy in conjunction with preconcentration and separation
steps to determine these compounds. It is possible to in-
crease the sensitivity by at least 2-3 orders of magnitude if
the reduction of semicarbazones or other azomethine deriv-
atives is monitored by twin cell potential sweep voltamme-
try.
In our laboratories, higher sensitivities can be achieved
using a twin cell set-up since it eliminates all of the non-
faradaic and faradaic currents not relevant to analysis
(11-15). In addition to the increase in sensitivity, this tech-