LITERATURE CITED (5) Harvey, C. E., “Spectroehemieal
Ac-
(1) Ayres, G. H., Berg, E. W., Anal.
Chem. 24, 465 (1952).
(2) Ibid., 25, 980 (1953).
(3) Ayres, G. H., Maddin, C. M., Ibid.,
26, 671 (1954).
(4) Gilchrist, R., Wichers, E., J. Am.
Chem. Soc. 57, 2565 (1935).
Quantitative Determination of Porosity
by X-Ray Absorption
G. L. CLARK and C. H. LIU
Department of Chemistry and Chemical Engineering, University of Illinois, Urbana, III.
The absorption method for
x-ray
measurement and control of porosity,
which involves penetration through
specimens with no discrimination be-
tween open and closed pores, has
been critically compared with the
pycnometric method in tests with com-
mercial rubber-composition storage
battery separators. Measurements by
both methods were in satisfactory
agreement. For the x-ray method,
after the linear absorption coefficient
is once determined for the complex
mixture, each specimen can be non-
destructive^ tested in a few minutes.
The x-ray method is reliable as well as
speedier and simpler than pycnometer
density measurements. It also per-
mits a rapid test of uniformity of
porosity.
property of porous texture,
The
which may often have great prac-
tical value, is possessed in varying de-
grees by many natural and manufac-
tured solid materials. The measure-
ment and control of porosity are often
difficult, inaccurate, and time-consum-
ing by older methods of density measure-
ment.
The porosity of a solid may be defined
as the volume of interstices measured as a
fraction of the apparent volume. Thus,
Fa -
V,
P =
CD
Va
where P is the porosity, Fa is the ap-
parent volume of the solid, and F, is its
true volume.
The most generally used method for
measuring porosity involves pycno-
metric determinations (1-3). The vol-
ume of the pores is calculated from the
increase in weight of a porous solid after
immersion in a penetrating liquid of
known density:
Received for review June 21, 1956.
Procedures,” p. 238, Applied Re-
search Laboratories, Glendale, Calif.,
1950.
(6) Keenan, R. G., White, C. E., Anal.
Chem. 25, 887 (1953).
(7) Noyes, A. A., Bray, W. C., “Qualita-
tive Analysis for the Rare Ele-
ments,” p. 133, Macmillan, New
York, 1927.
W3 TFi
-
P =
(2)
PVa
where IFi is the weight of sample before
immersion, W2 is its weight after immer-
sion, p is the density of the liquid, and
Va is the apparent volume of the sample.
Another method based upon the same
general principle is the gas absorption
method.
These methods are applicable only to
open pores which are accessible to the
liquid or gas. For closed porosity, the
solid must be ground into small par-
ticles to expose all pores. With such a
sample the true density of the solid ma-
terial can then be determined. From
this value and the weight, the true
volume of the solid can be calculated
and in turn, the porosity, from Equation
1. In all these methods long and diffi-
cult procedures are involved; often the
sample has to be destroyed during a
determination.
The x-ray absorption method is a
simple and efficient means of measuring
porosity. This application is by no
means a new one, for it has been used
with some success in this laboratory to
evaluate the porosity of storage battery
plates. There are also reports of
measurements of the gage of compres-
sible or porous materials, such as
leather, cellophane, cloth textiles, rub-
ber blankets, plastic films, paper, and
the like (4). The determination of the
porosity of sandstone in oil field work
has also been suggested. However, the
present work represents probably the
first highly critical comparison of clas-
sical and x-ray techniques, and is de-
signed to test thoroughly the reliability
of the latter as a routine, commercial
procedure for assuring constancy of
optimum porosity in fabricated rubber-
composition separators for storage bat-
teries now supplanting the fragile wood
separators used for so many years.
VOL. 29, NO. 10, OCTOBER 1957
cepted May 20, 1957. Condensed from a
dissertation submitted by Herbert J.
Belknap to the faculty of the Graduate
School of The University of Texas in par-
tial fulfillment of the requirements for the
degree of doctor of philosophy, August
1955. Portions presented at Tenth South-
west Regional Meeting, ACS, Fort Worth,
Tex., December 1954.
THEORY
The absorption law of x-rays is well
known:
2.303 log µ (3)
= -
¿0
where Ia is the intensity of the unab-
sorbed beam, I is the intensity of the
absorbed beam, µ is the linear absorp-
tion coefficient at a given wave length,
and X is the sample thickness. The
basic assumption is that there is no pre-
ferred orientation in the sample under
consideration, a condition which may
be tested by diffraction analysis.
When an x-ray beam of large cross
section passes perpendicularly through a
porous solid sheet, before the intensity
of the absorbed beam is measured the
beam will have swept through a known
apparent volume of the substance.
Specifically, this volume is the product
of the apparent thickness of the sample
and the area of the slit or of the detec-
tion device in direct contact with the
specimen, so that no beam divergence is
involved. It can easily be seen that
X X
_
X. Va
and X, X„ (1
=
P) -
(4)
where X, is the true thickness of the
sample, Xa is its apparent thickness, V,
is the true volume swept through by the
x-ray beam, Va is the apparent volume,
and P is the porosity of the sample.
The absorption law as applied to the
porous solid will then become
2.303 log y = —
µ (1 -
P) (5)
Hence,
1 + 2.303 log
P =
- -- µ . a (6)
If the value of the absorption coeffi-
· 1539
cient is accurately known, it will be pos-
sible to calculate P from experimentally
measured values of Xa, 7, and 70.
For a porous solid the main difficulty
in measuring the absorption coefficient,
unless the specimen is a pure chemical
substance for which tabulated values are
available, is the preparation of either a
nonporous sample of the same substance
or a sample of known and uniform
porosity. The latter alternative was
where Xt is the true thickness of the
sample in mils, X\ is the depth of the
holder in mils, W is the weight of the
sample in grams, p is the true density
of the sample, and Vk is the volume of
the holder in milliliters. W/p repre-
sents the true volume of the sample. It
is important that the grain size of the
sample be uniform so that the porosity
of the sample in the holder will also be
uniform and Xt will be constant through-
out the area of the holder.
linear plot obtained with a filtered x-
ray beam. It is true that, because the
x-ray is not strictly monochromatic,
samples of widely varying chemical
composition may not give this linear
relationship. However, it is always pos-
sible to establish, for a sample of a given
composition, an empirical curve relating
thickness and log 7/7o.
The linear absorption coefficient, µ,
of the sample was determined by cal-
culating X from Equation 7 and by us-
¡

chosen, An unfiltered beam is not suitable for ing Equation 3. The results are given
this determination, as the apparent ab- in Table I.
sorption coefficient will not be a constant Determination of Porosity. The
EXPERIMENTAL TECHNIQUES AND RESULTS
at various thicknesses of the sample be- same strips whose porosities had been
cause of differential absorption of the determined by the pycnometric method,
Density Measurements. As a typi- softer radiation; the value for the ab- were measured for porosity by the x-ray
cal manufactured product, the utility
andperformance of which depend upon sorption coefficient will be a function of absorption method. These strips were
correct porosity, a rubber-composi- thickness as well as of the intensity of simply placed in front of the slit while
tion storage battery separator (vul- the x-ray beam used. Figure 1, curve the absorbed beam intensities were being
canized rubber with filler such as lig- 1, shows a plot of log 7/70 vs. thickness measured.
with an unfiltered beam. Porosities were calculated from Equa-
nin) was the porous substance chosen To solve this problem, two convenient tion 6. The results are given in Table
to illustrate this method. A separa-
tor must permit diffusion of sulfuric alternatives are available. The first is II.
to filter the beam with the substance
acid, but insulate charged plates from
each other and resist short circuiting being measured at such a thickness that CONCLUSIONS
from the “treeing” of metallic lead in only the higher energy components of
the charged, negative plates. Hereto- the beam can pass through. In other The x-ray absorption method does not
fore, the adequacy of separators could words, measurements are to be made in seem to give a precision comparable to
be tested only over periods of time in
the lower region of curve 1, Figure 1. the classical method. However, the
The second alternative is to use a zir-
a battery.
conium oxide filter to obtain an approxi- porosity obtained by the classical
The separator was ground with a steel method is the over-all average of the
file into 200-mesh powder so that its mately monochromatic beam, as only
the a doublet of the molybdenum radia- whole-strip sample, whereas the values
true density could be measured. The determined by the x-ray absorption
tion will pass through the filter. In this
product obtained was tested colori- method are only the porosities of small
metrically for iron contamination with experiment, the latter alternative was
chosen. Curve 2, in Figure 1 shows the specific portions of the sample through
4,7-diphenyl-l, 10-phenanthroline (5).
The test was negative. The powder
was then dried over magnesium per-
chlorate under vacuum and weighed
into calibrated 5- and 10-ml. volumetric
flasks. The pycnometric density meas-
urements were made in the usual way
and gave an average of 1.293 grams per
ml.
Next, the separators were cut into
rectangular strips. The apparent vol-
ume of each strip was derived from the
product of width, length, and thickness
as measured with a micrometer to
±0.1 mil. These strips were dried
over magnesium perchlorate under
vacuum and weighed. Their true
volumes were calculated from their
weights and density. The porosities of
these strips computed from Equation 1
are listed in Table II for direct compari-
son with x-ray absorption results.
X-Ray Measurements. Appara-
tus. The source employed was a
molybdenum target, high intensity
tube operated at 40 kv. and 10 ma.
Intensities of the x-ray beam were
measured with a recently calibrated
Victoreen roentgenometer, with a
fixed slit and geometry with respect to
x-ray source and sample.
Determination of Absorption Co-
efficient. A Lucite powder-sample
holder was constructed with a volume of
4.578 ml. If a known weight of the
powder is placed in the holder and gently
shaken until the particles are evenly
distributed, the true thickness of the Figure 1. Absorption of x-ray beam in microporous rubber
sample can be calculated by the follow- storage battery separator
ing equation:
Molybdenum radiation, 40 kv., 10 ma,
XhW 1, Unfiltered
=
(7) 2. Filtered with zirconium oxide screen
PVk

1540 · ANALYTICAL CHEMISTRY

 These images were decidedly mottled in
Table I. Determination of Linear Absorption Coefficient appearance. Under these conditions it
Linear is remarkable that the acceptable pre-
True Absorption cision of the x-ray absorption method is
Sample True Thickness of Coefficient
Volume of Z‘ µ Mil"1 X
demonstrated by the rather close agree-
Weight, Sample, ,

log i7
Gram Sample, ML Mils Z, r per Minute” 0 10-= ment between the values obtained for
0.9561 0.739 70.1 30.1 ±0.2 -0.4310 1.42 the absorption coefficient; its applica-
0.4321 0.334 31.7 51.5 ± 1.5 -0.1978 1.44 bility is shown by the fact that the aver-
0.5540 0.428 40.6 44.0 ±1.0 -0.2656 1.50 age of the 10 determinations agrees well
Average of four readings for each run; exposure time, 2 minutes.^ with the results of pycnometry deter-
I o 81.2
= 2.7 r per minute. It was measured from time to time.
= Value given is minations.
average of eight measurements; exposure time, 2 minutes. The unique advantage of the x-ray
absorption method is its ability to
Table II. Determination of Porosity by X-Ray Absorption measure the uniformity of porosity in a
Apparent given sample. It is rapid and requires
Thickness of i
Ib Porosity no special treatment or destruction of
log 7
Sample, Mils Z, r per Minute” 40 X-ray Pycnometer the samples. The chief disadvantage is
26.8 91.0 ± 2.3 -0.0655 0.613 0.555 that it is not easily applicable to odd-
27.1 88.3 ±2.2 -0.0785 0.551 0.563
27.6 85 ±0.5 -0.0951 0.454 0.552 shaped objects of varying thicknesses.
27.1 87.5 ±1.7 -0.0825 0.518 0.553
26.2 85.9 ±2.2 -0.0905 0.475 0.556
62.4 69.6 ± 1.7 -0.1820 0.538 0.553 LITERATURE CITED
53.9 70.8 ± 1.5 -0.1744 0.488
81.5 60.8 ± 1.2 -0.2426 0.529 (1) Clark, G. L., "Applied X-Rays," 4th
108.6 56.9 ± 1.3 -0.2694 0.607 ed., p. 183, McGraw-Hill, New
134.8 48.8 ±1.2 -0.3356 0.606 York, 1955.
. 0.538 0.555 (2) Clark, G. L., Terford, H. C., Anal.
Chem. 27, 888 (1955).
“
Average of three readings for each run; exposure time, 2 minutes. (3) Franklin, R. L., Trans. Faraday Soc.
i/o 105.8 ± 3.4 r per minute. It was measured from time to time.
= Value given is 45, 274 (1949).
average of six measurements; exposure time, 2 minutes. (4) Garner, W. E., "Chemistry of the
Solid State," Academic Press, New
York, 1955.
(5) Smith, G. F., McCurdy, W. H., Diehl,
which the x-ray beam passes. If the was shown by microradiographs, which H., Analyst 77, 418‘(1952).
porosities of the samples are not uni- were obtained with the use of mono-
form within themselves, scattering of the chromatic copper radiation of wave Received for review June 7, 1956. Ac-
results is expected. The nonuniformity length 1.540 A. and enlarged 200X. cepted May 27, 1957.

Gas Chromatographic Separation of Some Permanent

Gases on Silica Gel at Reduced Temperatures
DALE H. SZULCZEWSKI and TAKERU HIGUCHI
School of Pharmacy, University of Wisconsin, Madison, Wis.

By useof 40- to 60-mesh silica gel
adsorbent at the temperature
as an
of dry ice-acetone, mixtures of such
permanent gases as oxygen, nitrogen,
nitric oxide, and carbon monoxide may
be satisfactorily separated and an-
alyzed. Separation cannot be effected
at room temperature, but excellent
resolution can be obtained in the
determination of a large number of
permanent gases at the reduced tem-
perature.
with a study of the
Concurrent
kinetics of decomposition of amyl
nitrite it became necessary to charac-
terize the gaseous decomposition prod-
ucts of the ester. An adsorbent was
required, suitable for gas chromato-
graphic analysis of gaseous mixtures
containing oxygen, nitrogen, nitric oxide,
carbon monoxide, nitrous oxide, and
carbon dioxide. Silica gel was success-
fully applied at reduced temperature for
this purpose.
The separation of permanent gases
through gas chromatography has been
the subject of several investigations,
all of which employ adsorbents at room
or elevated temperatures. Hydrogen,
carbon monoxide, oxygen, methane, and
other homologous hydrocarbon gases
have been separated on activated char-
coal (6, 9). Gaseous fluorinated hydro-
carbons have been resolved on silica gel
(7). Columns employing Molecular
Sieve were effective in separating hy-
drogen, carbon monoxide, oxygen, ni-
trogen, and methane, but apparently
they irreversibly adsorbed carbon di-
oxide (4, 8).
EXPERIMENTAL
The gas chromatography apparatus
was constructed in the usual fashion.
Samples of gas were introduced through
a rubber serum cap by a hypodermic
syringe.
The thermal conductivity cell was the
VECO M182. The bridge circuit was
constructed as described by the Victory
Engineering Corp. (10).
Throughout the investigation a 6-foot
spiral column of 6-mm. borosilicate
glass was employed. Forty- to sixty-
mesh silica gel obtained from Grade 12,
mesh size 28-200, Davison Chemical
Co. silica gel was used as an adsorbent,
after pretreatment. The column was
packed with silica gel, and was heated
uniformly with a Meker burner until
the sodium flame from the glass just
appeared. After the column was at-
tached to the apparatus and a flow of
helium established, it was again heated
with a Bunsen burner until the adsorb-
ent was free from moisture.
The carrier gas was helium under a
pressure of 10 pounds per square inch

VOL. 29, NO. 10, OCTOBER 1957 · 1541