QUANTITATIVE ANALYSIS BY

X-RAY DIFFRACTION
By K. NORRISH and R. M. TAYLOR
Division of Soils, C.S.I.R.O., Adelaide, South Australia.
[Received 18th April, 1962]
ABSTRACT
Certain minerals in soil clays may be directly estimated from diffraction
line intensity and the mass absorption coefficient of the sample to the
radiation used. The main advantages of the method described are that
no internal standards or calibration charts are required, and any diffraction line of the component to be estimated may be chosen. The
results obtained compare favourably with chemical determinations.
Orientation of particles during sample preparation makes the estimation
of some minerals very difficult. The uncertainty involved in choosing
the background level under a diffraction line is the chief source of error
in estimating small amounts of very fine-grained minerals.
INTRODUCTION

Because the intensity of an X-ray diffraction pattern is directly

proportional to the concentration of the component producing it,
when due allowance is made for absorption effects (Klug and Alexander, 1954), it has been possible to develop methods of quantitative
analysis based on diffracted intensities. The diffracted intensity of
any hkl reflection from any crystalline compound can be related to
the composition of the compound and its matrix, and to the instrumental geometry (Klug and Alexander, 1954; yon Engelhardt, 1961).
However, for any particular reflection, many of the parameters can
be reduced to a constant.
The following derivation of the relationship between diffracted
intensity and absorption is reproduced in part from Klug and Alexander (1954). Therein, it is demonstrated that if the incident and
diffracted X-ray beam enter and emerge symmetrically on the same
side of a 'thick' flat powder specimen,
I~ =KV
(l)
where Ix is the measured intensity of a diffraction line of a crystMline
component of the sample, V is the volume fraction of the component,
/~ is the linear absorpt on coefficient of the specimen, and K is a constant for any particular line of a particular mineral. This constant
depends on the incident X-ray intensity, the diffracting power of the
spacing being measured, the geometry of the instrument, etc. The
sample has to be sufficiently 'thick' to completely attenuate the incident beam.
98

99

QUANTITATIVE DIFFRACTION ANALYSIS

If Ois the apparent density of the specimen and p~ the true density
of the component being estimated, then
KX

/~--pxAx

(2)

where X=pxV/p-the weight fraction of the component being estimated, and A x =tx/p the mass absorption coefficient of the specimen.
If now the same diffraction line is measured on a standard sample
for which X is known and equal to S, then
KS
/~-(3)
psAs
Since ps=px, combination of equations (2) and (3) gives
x

AxI~S
A,ls
(4)
Generally a pure material can be selected as the standard, in which
case S = 1.
These equations were derived assuming that the crystallites of the
specimen were small enough not to give micro-absorption effects
(Brindley, 1945), an assumption that will be justified for clay separates of < 5 tL equivalent spherical diameter. With larger particles,
the incident and diffracted beams may be attenuated to different
degrees in the mineral to be estimated and the matrix, and the use of
the average measured mass absorption coefficient in equation (4)
would not necessarily give the correct estimation. The maximum
permissible crystallite size at which micro-absorption effects are
still negligible will depend on the difference between the absorptions
of the component and the matrix to the radiation being used. Von
Engelhardt (1961) has classified the particles of a sample by the product of their particle size (in cm.) and their linear absorption coefficient to a particular radiation. When this product is Jess than
0-01, no correction for micro-absorption is necessary.
Most commercial diffractometers have a geometry such that the
above equations are satisfied and the measurement of Ix and Is with
them presents no problem in principle. Leroux, Lennox and Kay
(1953) used equation (4) to determine quartz in various mixtures,
using a diffractometer to measure Ix and Is. Ax and As were calculated from the measured absorption coefficient of the samples to
shorter 'white' radiation. In principle this method cannot be used
to obtain absorption coefficients with any high or constant degree of
accuracy for two reasons: (a) because the beam is not monochromatic, the absorption coefficient will change with the sample thickness; (b) if the absorption coefficient is measured for any wavelength
other than that used in measuring diffracted intensities, the presence
of any element with an absorption edge between the two wavelengths
would give rise to serious errors.
Leroux (1957) in later work used monochromatic Mo Ka radiation
(reflected from the 101 plane of quartz) instead of the white radiation

I00

K . N O R R I S H A N D R . M. T A Y L O R

direct from a Cu target, to measure A ~ and As. Using this technique,

he estimated quartz with a standard deviation of 2 per cent. from the
nominal values. Short wavelengths, such as Mo Ka, are more
satisfactory for absorption measurements because much thicker
samples can be used, but these wavelengths do not give sufficient
dispersion for diffraction studies of clay minerals.
Despite the simplicity of equation (4) and the fact that its application does not involve the tedium of making calibration curves with
internal standards '(Ballard, Oshry and Schrenk, 1940; Klug, 1953),
or with artificial samples, it has been used very little. The various
other methods of analysis (internal standards, etc.) are essentially
indirect methods of allowing for A~/A~. Leroux, Lennox and Kay
(1953) used Ax and As but did not measure these quantities directly,
possibly because of difficulties associated with making specimens
thin enough for direct measurement.
Since not all the advantages of applying equation (4) as a method
of analysis are immediately obvious, they are worth brief mention.
For most estimations, a method in which As and As are measured
eliminates the need of any sample pretreatment other than that
necessary to obtain a suitable diffraction trace. Moreover, because
Ax and As do not occur as angular functions, as they do in photographic techniques, any diffraction peak in a routine trace may be
selected for the measurement of Ix. This is particularly important in
the analysis of rocks and soils where, because of the numbers of
minerals which may occur and the complexity of their patterns, there
is a high probability that any preselected line may suffer interference
from adjacent or coincident lines. The technique therefore has the
big advantage that the selection of a suitable line for measurement
can be made after the diffractometer trace has been obtained.
In the present study it is shown that satisfactory analyses can be
made using Cu or Co radiations for both absorption and diffraction
measurements.
EXPERIMENTAL

Methods. In preliminary experiments a Norelco high-angle

diffractometer using a Geiger-counter detector in conjunction with a
ratemeter and recorder was used to estimate I~ and Is. This equipment has since been modified by the addition of a pulse-height
analyser and the Geiger counter has been replaced by a scintillation
detector. Using the scintillation detector, counting losses are less
and non-monochromatic radiation can be partially eliminated, thus
increasing the line to background ratio.
A monochromatic beam of high intensity for absorption measurements, was obtained by putting single-crystal slabs (e.g., quartz,
lithium fluoride, or sodium chloride) or oriented powder specimens
(e.g., graphite) in the sample position of the diffractometer, the detector being set to the 20 position corresponding to the reflecting
plane. The absorption of the sample was measured by placing it ia

QUANTITATIVE DIFFRACTION ANALYSIS

10I

front of the receiving slits of the detector and measuring the reduction in intensity.
It is very desirable to use a reflecting plane which has very weak
second and third order reflections, otherwise it is necessary to run the
X-ray tube at a low kilo-voltage to avoid contaminating the monochromatic beam with harmonics.
Sample Preparation. In general, the samples analyzed were < 5Vfractions. For the various artificial mixtures the individual components of the required particle sizes were mixed together by grinding.
Specimens for diffractometry were prepared by lightly pressing the
powder into rectangular metal holders, 2 cm 1 cm (Klug and
Alexander, 1954). Sometimes minerals with a pronounced fibrous
or platy habit became preferentially oriented during this treatment,
in which case the diffracted intensity of a peak was no longer linearly
related to the mineral concentration. It was found that orientation
effects could be reduced a little if, during the preparation, the front
surface of the specimen was pressed against a surface of ground glass
or coarse paper rather than a polished surface, as this preserved some
degree of randomness in the surface packing.
Specimens for the measurement of the mass absorption coefficients
were prepared by pressing the powdered sample into a 89in. (1.27 cm)
diameter hole in an ~ in. Perspex holder. Pressures varying between
200 and 2000 kg/cm 2 were necessary to ensure self supporting samples,
(Preferred orientation does not affect this determination.) Samples
of uniform thickness were obtained with the aid of jigs. The sample
holders were weighed before and after loading. Samples weighing
less than 0.03 g are difficult to make, and 0.07-0.10 g is generally
required.
When a sample cannot be made sufficiently thin, it may be diluted
with a material with low absorption, such as boric acid. The
measured absorption coefficient must then be corrected for the
amount of diluent added. This type of mixture is particularly prone
to errors from micro-absorption effects, so great care must be taken
to ensure complete mixing of sufficiently fine particles. The measurement of the absorption coefficient is generally made on duplicate
samples.
Measurement of Mass Absorption Coefficient. If a sample of
thickness I is inserted in a monochromatic X-ray beam of intensity
Io, the attenuated beam, intensity I, is related to the incident beam
intensity by the relationship

I-- Ioexp( -tzl)

so that measurement of I and Io determine txl. The weight of the
sample and its area (1.27 cm z) gives its mass/cm 2, pl, and the mass
absorption coefficient, A=tz/p--izl/pl.
Ratios of I/Io as low as 3 10 -5 (/xl= 10)* could be measured to
*These measurements were made using fluorescent radiation. It is doubtful
if radiation taken direct from an X-ray generator could give such results as it h a s
associated with it m u c h m o r e 'white' radiation.

102

K. NORRISH AND R. M. TAYLOR

give accurate measurements of A. Table 1 shows some mass absorption measurements compared with those calculated from
standard tables.
TABLE 1--Comparison of measured and calculated mass absorption coefficients.
Cu K a

Sample
Aluminium
Quartz, SiOz*
He natite, FezO3*
Goethitet
Kaolins
Dolomite, CaMg(CO3)2*
Calcite, CaCO3*

Co Kct

Meas- Calc~ 9 Meas- Calcuured

latec
ured
lated
48.7
36.1
-! 87
32.0

48.9
35-0
230
200
31.6

75"0
55"1
44 "7
43 '4
48 "0
69
108

73.4
54.8
47.7
43.7
47.0
71
106

Fe K a
Meas- Calcuured
lated
94-5
69 '2
56.4
53.0

93.8
67.6
56.3
51.4

*Chemical composition assumed to correspond to formula.

tAnalysis: Fe203 86"7, H20, 13.2 Si02 0.15.
SAssumed: Si02 45, A1203 40.5, H20 14"5.

The deviations between calculated and experimental absorption

coefficients are generally less than the uncertainty in published mass
absorption coefficients of the elements. The data available on
experimentally determined absorption coefficients (Compton and
Allison, 1935; Hodgman, Weast and Selby, 1956) are very incomplete so that calculated coefficients (Henry, Lipson and Wooster,
1953), had to be used and for low atomic number elements the latter
often disagree seriously with the former. Mass absorption coefficients could generally be measured with a reproducibility of about
1 per cent. and counting errors were reduced to 1 per cent. The main
source of error in the determination is the deviation of the sample
from a uniform parallel sided slab (error in l). Sample preparation
and the measurement of mass absorption requires only a few minutes.
Measurement of Line Intensities. The most accurate method of
measuring diffraction intensities is to take a large number of counts
at the required angle. Then, if sufficient counts are taken, the accuracy is limited by output stability of the X-ray set--and this can
be reduced to a small fraction of 1 per cent. If no other lines lie
near that being measured and if the background in this region is flat,
there is no problem in obtaining an accurate measure of the peak
height of the line above background.
For complex natural mixtures, however, the integrated area (or a
modification of this) was chosen as the most convenient measure o f / ,
for several reasons. In the analyses of soils and rocks, the background is rarely flat so that averaging the background on either side
o f the line does not necessarily give an accurate estimate of the line

QUANTITATIVE DIFFRACTION ANALYSIS

103

background, particularly if other lines lie near that being measured.

In these instances it is desirable to see the intensity distribution over
an angular region on either side of the line, because the background
estimation requires some judgement. If diffraction lines suffer
broadening because of small particle size or other causes, the measurement of peak height will not give a good estimate of line intensity
(line broadening is common in soil minerals). If the crystallite size
of specimens is not sufficiently small (< 5t~), relatively large errors can
occur in the measurement of the peak height of lines due to the small
number of particles contributing to diffraction at a particular angle
(Klug and Alexander, 1954). Many more crystallites are considered
when the line intensity is integrated over a small angular range and
the errors will therefore be reduced.
The integrated intensity can itself be measured by two methods,
either by measuring the area enclosed by the peak and the estimated
background, or by taking the product of the maximum peak height
and the peak width at half maximum height.
There are, however, further problems associated with the accurate
measurement of peak areas. A diffraction line has the profile of a
tailed triangle (Fig. 1) for which the level of the base (background) is

40

39
2e

38

37

DEGREES

FIG. 1--Profile of a typical X-ray diffractionline, the 130 line of goethite.

the most uncertain feature, whilst the area changes markedly with
small changes of background because of line width in this region.
To overcome the large errors which might thus occur, and to take
cognisance of line width, the product of the peak height and the width
at half peak height was chosen as the most satisfactory compromise

104

K. NORRISH AND R. M. TAYLOR

:for the measurement of L Table 2 shows the errors introduced into

the various measures of line intensity by purposeful errors in background.
TABLE2--Variations in line intensity due to background uncertainty
(assumed 5% of peak height).
Method of Measuring line intensity
Mineral and line width

Peak
height

Goethite 130 line

Width at ~-peak height 0-3 ~
Quartz 101 line
Width at 89peak height 0.175 ~

+5%
--5%
+5%
-5%

Area

Peak height width

at 89peak height

+22.4~

+12"2~

--16-1%

+ 3"7%
--13 '2%

-15.8%

--

8"8%

I n o b t a i n i n g diffractometer traces for m e a s u r e m e n t the scanning

speed o f the d e t e c t o r a n d the time c o n s t a n t o f the r a t e m e t e r were
a d j u s t e d so that line profiles were n o t altered appreciably.
RESULTS AND DISCUSSION
Fig. 2 shows experimental values o f Ix~Is for C o K a a n d C u K ~
radiations, for artificial mixtures o f goethite a n d kaolinite, and it is
1.0

O8

~C
06

~9
.=.

~/

04

02

//84

",/

0.2

>~

04

06

0.8

tx/i s

Fzo. 2---Variatiort of Ix~Is with goethite content for Co and Cu radiations.

Continuous lines show the predicted relationship; experimental points.

QUANTITATIVEDIFFRACTIONANALYSIS

105

seen that these values lie close to the curves predicted by equation (4).
The two curves are quite different because the mass absorption
coefficients of kaolinite and goethite for Cu Ka differ widely (32 and
187 respectively) whereas for Co Ka radiation they are almost the
same. Hence there is an almost linear relation between I~/I~ and
goethite concentration for Co Kct.*
In obtaining the theoretical curves for Fig. 2, A x was calculated
from the relationship,

Ax=xAg + (1--x)A.,
Ag and AK being the mass absorption coefficients of goethite and
kaolinite, and x the proportion of goethite present.
TABLE3--Calculated and nominal compositions for various synthetic mixtures.

Mixtures
in Kaolin

Nominal
composition
(%)

Sample 1

50 Goethite

Sample 2
Sample 3

Calculated comp. (~)

Using
areas

49.2

5 Haematite
50 Quartz

47
50.5

<{%

Sample 4

20 Quartz

$20-2

s249.4
o.,

Sample 5

50 Goethite

Sample 6

25 Haematite
25 Goethite
37.5 Haematite
25 Quartz

%22

48.2
23.2
f24.6"
\22"2
37"5
21

Line

Using
products

130
111
102
101
112
10l
112
130
111
102
130
lll
102
101

4'25

$21.5
~20.4

.5
(~'5
20"7

*Calculatedfromthe intensityof the compound peak at 2"69~ by subtracting

duo to the 102 line of the hematite component

the

intensity

Table 3 shows the results obtained by the application of equation

(4) to some artificial mixtures, the quantities As, Is, Ax and Ix being
determined experimentally. The agreement between the actual and
determined amounts is satisfactory, in that the errors are of the same
order as errors in A and L Analyses made using different lines o f
a diffraction pattern gave good agreement, even when the lines have
a large angular separation (Table 3).
Table 4a presents the analyses of some soils and clays for goethite
and haematite, these particular results being given for comparison
*This is a very good reason, apart from the high background associated with Ctt
radiation, for using Co radiation on soil samples high in iron.

106

K. NORRISH AND R. M. TAYLOR

with i n d e p e n d e n t chemical estimates of the total Fe203. Table 4b

compares the percentages o f gorceixite a n d crandallite measured by
diffraction methods with those calculated from the P content. These
calculations were made assuming that the minerals had a n invariant
composition. The two methods of estimation agree well b u t several
factors prevent a n absolute comparison. The chemical variability
o f gorceixite prevents accurate estimations from the p h o s p h o r u s
TABLE4a--X-ray diffraction estimations of iron oxide minerals in soils.
Sample
Cookls. whole soil
...
West. Aust.
< 2/* Lateritic . . . . . .
West. Aust.
< 2 1. Lateritic . . . . . .
West. Aust.
< 2 1. Lateritic . . . . . .
Victoria
<5t*

.........

Tasmania
< 0.51. . . . . . . . . .
Barbados W. I.
< 2 1. Terra Rossa

...

Diffraction
estimation
(%)

Free FezO3
(%)

Fe203
accounted for
(%)

Goethite 42

49 "5*

76

29"6t

91

Goethite 39

37 "8"["

93

Haematite 1.2
Goethite 2

4'6

65

Haematite 6
Goethite 3

9.5

92

Goethite 3.5

79

Goethite 6.2

7.5

74

Goethite 30

*A small amount o f ilmenite or haematite was identified from diffraction photographs.

i ' A very small amount of the iron of these clays is probably present as ilmenite.

TABLE4b---Estimation of gorceixite in three fractions of a soil.

Gorceixite (%)
Sample

9 '
By diffraction

Calcuiated
from total
P content

Ratio of
estimations

Whole Soil
......
0.5--5 ~ .. . . . . . . .
0.5--5 1. after HF treatment

3.2
12.5
70

2.6
11.5
56

1-23
1.10
1.25

content, whilst this same variability means that the standard mineral
is n o t identical with that of the soil, so that absolute estimations
c a n n o t be m a d e accurately by diffraction methods. Most complex
m i n e r a l s - - p a r t i c u l a r l y those forming m u l t i - c o m p o n e n t solid solutions
- - s h o w such chemical variability and are therefore difficult to analyze
absolutely. Most clay minerals fall into this category. The failure
to account for m u c h o f the measured free Fe203 in some samples,
(Table 4a), can also be attributed to a similar cause. Norrish a n d

107

QUANTITATIVE DIFFRACTION ANALYSIS

Taylor (1961) have shown that aluminium isomorphously replaces

iron in soil goethites. Replacements up to 25 mole per cent. have
been measured and there are corresponding changes in the diffracted
intensities. The diffraction line used to measure Ix for goethite in
these soils was the 111 reflection whose intensity varies linearly with
the degree of substitution. When correction is made for this factor
the diffraction estimates agree better with the chemical determination.
Preferred orientation of particles during the preparation of the flat
sFecimen used with focusing diffractometers may also give rise to
serious errors. Materials which have a good cleavage or a platy or
fibrous habit are very prone to orientation effects. In analyses for

150

12o

9o

o
60

(11,)

(13o)

(,',1

NON- ORIENTED

(,ooo ,,~,)
L

43

a"

'

..a

42
~O

' " L.~-.-J

3q
DEGREES
30

3~

39

<.3
20

38

DEGREES
3b

FIG. 3 - - T h e effect o f orientation on the relative intensities o f geothite 130 and

111 diffraction peaks.

goethite orientation effects were observed, the 111 line decreasing

and the 130 line increasing in intensity with increased orientation.
Fig. 3a demonstrates the increase in intensity of the 130 and an
associated decrease in the 111 peaks after pressing the sample on a
fiat surface to a pressure of 4000 p.s.i. Fig. 3b shows the height of
two goethite peaks when the sample was prepared under a slight
pressure on a filter paper surface, which tends to eliminate orientation. Satisfactory results were obtained only from those specimens
for which the intensity ratio of the 111 and 130 lines was the same as
that of the standard. Here, the ratio used was 1.43 and probably
corresponds to random or almost random packing. This value agrees

108

K. NORRISH AND R. M. TAYLOR

well with the ratio of 1.38 calculated from the structure of goethite.
With minerals of more pronounced habit it has not been possible to
make specimens in which the particles are even approximately
randomly orientated. The degree of orientation of a mineral in
samples prepared by identical methods will vary with its particle
shape and size. Table 5 gives results for various kaolin minerals,
TABLE 5--Orientation in kaolins as measured by the intensity ratios of the
002 and 060 lines.

Sample
Kaolinite
Kaolinite < 2 t*
Kaolinite < 2 t~
Kaolinite
Kaolinite
Dickite
Hallyosite*
Halloysite*
Halloysite*

Origin
Mt. Crawford
Sth. Aust.
West Aust.
West. Aust.
McNamee, Sth.
Carolina
Germapy
N.S. Wales
Black Spur,
N.S. Wales
Tasmania
Bedford,
Indiana

Area o f
002 line

Area o f
060 line

55

18'5

2.99

174
103 "5
56.1

10.6
1l
24 "9

16"4
9"4
2"25

202
138
69 "9

6 '5
15.2
28.3

31 .I
9'1
2 "46

78
62.1

32.5
24-7

2-4
2.56

Ratio

*All haUoysites were measured after being oven dried for 4 hours at 105~

orientation being measured by the intensity ratio of the 002 to the

060 line. The halloysites, which are tubular in habit, give the lowest
values for this ratio and are probably nearly randomly oriented.
Even within the one specimen it is rash to assume that various clay
minerals will have the same degree of orientation, an assumption
which is implicit in many recent clay and soil analyses made using
diffractometers. A powder diffraction photograph of an oriented
flake of a soil clay clearly shows how the various clay components
may be very differently oriented.
Though there does not yet appear to be any reliable method of
overcoming orientation problems, the authors are experimenting
with various techniques for either overcoming orientation or allowing
for it. A satisfactory technique, however, will probably require more
elaborate methods of sample preparation and subsequent analysis
than those described here.
CONCLUSIONS

From the results presented it is clear that this method gives very
good results on artificial samples or when estimating large amounts
of a mineral under ideal conditions. The accuracy will normally be
less when analyzing an unknown sample, the limit being set by nature

QUANTITATIVE DIFFRACTION ANALYSIS

109

of the mineral, its orientation, micro-absorption variability, concentration, and the measurement of the diffracted intensity above
the background. However, these problems are present in any
method of quantitative diffraction analysis.
Even considering these limitations this method gives results as
good as those obtained by other methods and avoids the necessity
of calibration curves (which imply a knowledge of the sample) or
additions of an internal standard which itself may introduce into
an otherwise satisfactory sample micro-absorption or orientation
effects.
Acknowledgements.--Dr E. W. Radoslovich of this Division is thanked for his
critical reading of the manuscript.

REFERENCES
BALLARD, J. W., OSHRY, H. i., and SCHRENK,H. H., 1940. Rep. Invest. U.S.
Bur. of Min., No. 3520.
B~NOLEY, G. W., 1945. Phil. MAR., 36, 347.
COMPTON, A. H., and ALLISON,S. K., 1935. X-ray in Theory and Experiment.
Van Nostrand, New York.
HE~Y, N. F. M., LXPSON,H., and WOOSTER,W. A., 1953. The Interpretation
of X-ray Diffraction Photographs. Macmillan, London.
HODGMAr~,C. D., WEAST,R. C., and SELBY,S. M., 1956. Handbook of Chemistry
and Physics. Chemical Rubber Publishing Co., Ohio.
KLUG, H. P., 1953. Analyt. Chem. 25, 704.
KLUG, H. P., and ALEXANDER, L. E., 1954. X-ray Diffraction Procedures.
Wiley, New York.
LEROLrX,J., LENNOX,D. H., and KAY, K., 1953. Analyt. Chem., 25, 740.
LEROtrX, J., 1957. Norelco Reporter, 4, 107.
"CON ENG~LHARDT,W., 1961. Science and Industry (Philips Electrical Industries
Ltd.), 8, 2.
NORRISHK., and TAYLOR,R. M., 1961. J. Soil Sci., 12, 294.