Pure&App/. Chem.,Vol.61, No.9, pp. 1643-1656,1989.

Printed in Great Britain.

@ 1989 IUPAC

INTERNATIONAL UNION OF PURE

AND APPLIED CHEMISTRY
ANALYTICAL CHEMISTRY DIVISION
COMMISSION ON MICROCHEMICAL TECHNIQUES AND
TRACE ANALYSIS*

PRECIPITATION OF MAJOR
CONSTITUENTS FOR TRACE
PRECONCENTRATION : POTENTIAL
AND PROBLEMS'

Prepared for publication by

ALAN TOWNSHEND' and EWALD JACKWERTH2
'School of Chemistry, University of Hull, Hull HU6 7RX, UK
*Ruhr-Universitat Bochum, Faculty of Chemistry, PO Box 102148, D-4630 Bochum, FRG

* Membership of the Commission during the period (1985-1987) this report was prepared
was as follows:
Chairman: B. Griepink (Netherlands); Secretary: D. E. Wells (UK); Titular Members: K.
Biemann (USA); E. Jackwerth (FRG); A. Lamotte (France); Z. Marczenko (Poland); Yu.
A. Zolotov (USSR); Associate Members: K. Ballschmiter (FRG); R. Dams (Belgium); K.
Fuwa (Japan); M. Grasserbauer (Austria); W. H. Gries (FRG); M. W. Linscheid (FRG);
H. Muntau (Italy); M. J. Pellin (USA); B. Ya. Spivakov (USSR); A. Townshend (UK); D.
G. Westmoreland (USA); National Representatives: R. Gijbels (Belgium); Z.-M. Ni
(China); M. J.-F.Leroy (France); S. M. Khopkar (India); A. D. Campbell (New Zealand);
A. Cedergren (Sweden); E. A. Terent'eva (USSR); J. M. Ottaway (UK)**.
** Deceased.
Series Title: Separation and Preconcentration of Trace Substances: I1

Republication of this report is permitted without the need for formal IUPAC permission on condition that an
acknowledgement, with full reference together with IUPAC copyright symbol (0 1989 IUPAC), is printed.
Publication of a translation into another language is subject to the additional condition of prior approval from the
relevant IUPAC National Adhering Organization.
 Precipitation of major constituents for trace
preconcentration: Potential and problems

-
S , m ~ , y The success o f the separation o f trace components by pre-
c i p i t a t i o n o f the matrix depends not only on the q u a n t i t a t i v e l y definable
properties o f the matrix and the trace constituents, but also on many
marginal conditions. These produce e f f e c t s which cannot as a r u l e be
described numerically, and which impede the development o f general rules
f o r the choice o f appropriate working parameters.

I n t h i s report an attempt is made t o derive simple rules f o r trace

enrichment. The application o f the rules is i l l u s t r a t e d w i t h examples
from the l i t e r a t u r e . A compilation o f publications i s tabulated dealing
with the application o f matrix p r e c i p i t a t i o n t o the simultaneous
separation o f several elements from pure metals.

1. INTRODUCTION

Nearly a l l methods t h a t are applicable t o trace preconcentration make use o f the d i f f e r e n t

d i s t r i b u t i o n o f compounds between two e a s i l y separable phases. For t h i s purpose, the phases
are e i t h e r formed by the components t o be separated, a f t e r transformation i n t o appropriate
compounds, o r a u x i l i a r y phases are produced between which the d i s t r i b u t i o n e q u i l i b r i a are
established. I n general, the effectiveness o f the recovery o f trace components has t o be
determined. Even when the equilibrium constants o f the d i s t r i b u t i o n reactions, usually
involving several p a r t i a l e q u i l i b r i a , are known, the success t o be expected can usually only
be predicted roughly. Experience shows t h a t the smaller the trace concentration, and the
larger the difference i n concentration between the trace component and matrix, the less
satisfactory are the theoretical predictions o f d i s t r i b u t i o n e q u i l i b r i a ( r e f . 1).

Precipitation, one o f the oldest methods o f separation, is used i n trace separation methods.
The sample solution serves as an a u x i l i a r y phase, w i t h i n which the second phase i s produced
by adding a reagent so t h a t c e r t a i n components o f the sample are more o r less s e l e c t i v e l y
precipitated. When traces are t o be determined, an a u x i l i a r y ( c o l l e c t o r ) phase must normally
be precipitated simultaneously so t h a t there i s s u f f i c i e n t p r e c i p i t a t e containing the trace
component t o be f i l t e r e d o r centrifuged conventionally. I n p r e c i p i t a t i o n s o f t h i s kind,
calculation o f the extent o f p r e c i p i t a t i o n o f a trace component on the basis o f tabulated
s o l u b i l i t i e s normally gives very inaccurate predictions. Deviations from calculated
s o l u b i l i t y e q u i l i b r i a a r i s e p a r t i c u l a r l y a t the trace level from a v a r i e t y o f side reactions,
and interaction with sample components and container surfaces which normally would be
considered i n e r t . The rate o f p r e c i p i t a t i o n also greatly influences the e f f i c i e n c y o f trace
p r e c i p i t a t i o n and, unless slow p r e c i p i t a t i o n is achieved, d i s t r i b u t i o n s based on equilibrium
calculations cannot be expected>t o be v a l i d (ref. 2 ) . Nevertheless trace separation by
coprecipitation i s amongst the most useful methods f o r multielement separation from a large
variety o f sample materials, because o f the high concentration factors achievable and i t s
relative simplicity.

The effectiveness of trace separation methods based on the p r e c i p i t a t i o n o f the main

components must be judged quite d i f f e r e n t l y . I n such cases, the same co-precipitation e f f e c t
may now be the cause o f losses o f trace components. I n the course o f time, rules as t o the
choice o f p r e c i p i t a t i o n conditions have been formulated, on the basis o f experimental
observation, which must be adhered t o for achieving quantitative separations ( r e f . 3 ) . The
successful separation o f the matrix by p r e c i p i t a t i o n therefore requires knowledge o f l i k e l y
perturbing factors and o f possible ways t o removing them o r a t least minimizing them. For
t h i s , i t i s important t o know the nature and concentratton o f the traces which are t o be
separated.

I n the present report the most important observations concerning p r e c i p i t a t i o n and

coprecipitation reactions are collated and discussed. The goal is an attempt t o obtain
rules, the systematic observation o f which w i l l render the success o f trace separation by
matrix p r e c i p i t a t i o n less dependent on chance. These rules are i l l u s t r a t e d by selected
applications. F i n a l l y procedures for multielement recovery from pure metals by matrix
p r e c i p i t a t i o n are tabulated. The nomenclature o f methods o f p r e c i p i t a t i o n and
coprecipitation has been published prevlously (ref. 4,5).
1644
 Precipitation of major constituents for trace preconcentration 1645

2. PROPERTIES OF PRECIPITATED COMPOUNDS

For gravimetry the p r e ci p i ta te s produced should be s u f f i c i e n t l y pure t o give no anal y t i c al
error. This i s also t r u e f o r the separation o f traces by matrix prec i pi t at i on. Extensive
investigations o f various stages o f p r e c i p i t a t e formation (supersaturation, nucleation,
c r y s t a l growth, ageing) ( r e f. 6-61 have l e d t o an understanding o f t he influence o f
conditions on p a r t i c l e si ze and p r e c i p i t a t e p u r it y . I n general, prec i pi t at es o f larger
p a r t i c l e size are o f greater p u r i ty.

2.1 Solubility
The calculation of so l u ti o n e q u i l i b r i a o f p r e ci pi t at es requires knowledge o f the s o l u b i l i t y
and s o l u b i l i t y product (Ko) o f the p r e ci p i ta te d compound. The s o l u b i l i t y product, i n turn,
requires information on the stoichiometry and composition o f the compound. This I s
problematical with many precipitates, p a r t i c u l a r l y "hydroxides" and sulphides, where the1 r
composition and structure vary wi th the p r e c i p i t a t i o n conditions ( r e f . 6,9,10). Particle
size and ageing processes also s i g n i f i c a n t l y a f f e c t t he s o l u b i l i t y o f a prec i pi t at e. Similar
problems arise i n the d i sso l u ti o n o f precipitates, where side reactions (e.g. hydrolysis,
formation of complexes) can also be expected, and i n general, p r e c i p i t a t i o n and di s s ol ut i on
o f a given compound cannot be assumed t o be r e ci procal (ref . 11 ).

The application o f KS values t o trace a n a l yti ca l separation methods must therefore be viewed
w ith caution, since i n the d e f i n i t i o n o f s o l u b i l i t y product, ideal equilibrium conditions are
assumed. Furthermore the p r e c i p i t a t e may dissolve as molecules as well as ions ( r e f . 1 2 ) ,
but such s o l u b i l i t y i s not measured by the conductimetric o r potenticmetric techniques of t en
used t o evaluate s o l u b i l i t y products. Care must therefore be taken t o ensure t h a t the
s o l u b i l i t y values take i n t o account both i o n i c and molecular s o l u b i l i t y , i.e. s o l u b i l i t y as
ionic species and as undissociated molecules, respectively. I t i s of t en qui t e l i k e l y t h a t
the molecular s o l u b i l i t y o f a sparingly soluble compound i s much greater than the i oni c
s o l u b i l i t y . This i s especially t r u e f o r the almost insoluble sulphides and hydrated oxides
(re f. 111, where not only molecular s o l u b i l i t y but soluble complex formation make an
important contributi o n t o s o l u b i l i t y .

2.2 Particle size

The p a r t i c l e size o f a p r e c i p i t a t e i s governed by the r e l a t i v e rates o f nucleation and
p a r t i c l e growth, as well as by the concentration o f p r e c i p i t a t i n g species. Nuclei are the
smallest p a r t i c l e s o f p r e c i p i t a t e which can grow spontaneously. Their formation i s termed
nucleation, and i s a necessary i n i t i a l stage i n the p r e c i p i t a t i o n process. Detailed
considerations of t h i s process have been given by various authors ( r e f . 6,7,13,14). Although
d i f f e r e n t nucleation mechanisms have been proposed, they a l l require concentrations o f
p r e c i p i t a t i n g species s i g n i f i c a n t l y i n excess o f t h e i r saturation s o l u b i l i t y (i.e.
appreciable supersaturation) i n order f o r nucleation t o begin. Additionally, nucleation may
involve only p r e c i p i t a t e species (homogeneous nucleation) o r may involve sub-microscopic
impurity p a r t i c l e s (heterogeneous nucleation). The former i s a higher energy process,
requires a much higher concantration o f p r e c i p i t a t i n g species than the l a t t e r , and tends t o
produce a much greater concentration o f very small p r e c i p i t a t e part i c l es . I f solutions are
s u f f i c i e n t l y concentrated, c o l l o i d a l suspensions are obtained.

I n order t o produce large p r e c i p i t a t e p a r ti cl e s, therefore, homogeneous nucleation should be

avoided o r minimized. This can o fte n be achieved by r e s t r i c t i n g the concentrations o f the
species involved i n p r e c i p i t a t e formation but f o r many compounds, such as hydrated oxides o r
sulphides, homogeneous nucleation occurs a t such low concentrations as t o make t h i s
impractical. I n such situations, the use o f p r e c i p i t a t i o n from homogeneous solution, which
greatly r e s t r i c t s the instantaneous concentrations o f prec i pi t ant , can be very benef i c i al
( r e f . 15).

The s o l u b i l i t y o f very small p a r t i c l e s ( < 0.1 im diameter) i s greater than t h a t o f large

p a r t i c l e s o f the same material. Therefore, i f small p r e c i p i t a t e p a r t i c l e s are obtained, i t
i s o ften possible t o increase t h e i r si ze by an "ageing" process, because when a suspension i s
heated, the small p a r t i c l e s tend slowly t o dissolve and redeposit on the larger, less soluble
p articles.

2.3 Purity
The incorporation i n t o p r e ci p i ta te s o f other components o f a sample s ol ut i on can occur i n a
number o f ways, the most important being:
(a) mechanical or adsorptive inclusion o f the mother s ol ut i on w i t h i n disordered
l a t t i c e regions o r pores o r enclosed spaces w i t hi n c r y s t a l aggregates o r gels;
(b) adsorption o f ions o r molecules on the p a r t i c l e surface;
(c) inclusion o f "foreign" ions i n the cr ysta l l a t t i c e (formation o f mixed c ry s t al s );
(d) exchange o f surface l a t t i c e ions by "foreign" ions.
The inclusion o f foreign ions i n t o the cr ysta l l a t t i c e i s thermodynamically predictable (see
3.3). However, such predictions are based on equilibrium conditions as i s implied i n
s o l u b i l i t y product calculations. Thus, as the r at e o f p a r t i c l e growth increases, there i s an
1646 COMMISSION ON MICROCHEMICAL TECHNIQUES AND TRACE ANALYSIS

increased deviation from equilibrium conditions, and decreased discrimination between the
p r e c i p i t a t i o n o f the major component and "foreign" species (ref. 16). Thus, species which
are being concentrated i n the p r e c i p i t a t e by co-precipitation are less e f f i c i e n t l y separated
from the matrix under conditions o f rapid p a r t i c l e growth such as are achieved a t high
reactant concentrations. Likewise, attempts t o p r e c i p i t a t e the matrix w h i l s t leaving trace
species i n solution are less e f f i c i e n t under conditions o f rapid p a r t i c l e growth.

3. CAUSES OF PRECIPITATE CONTAMINATION

The main goal o f the early studies o f coprecipltation was t o establish &I&& ions are
coprecipitated under c e r t a i n conditions and &. The question as t o which elements are DQ~;
coprecipitated, which i s more important t o the trace analyst, was deemed less interesting.
As i s shown below, however, there are several very e f f i c i e n t procedures f o r multi-element
concentration i n which the matrix i s precipitated t o separate i t from trace analytes. It i s
worthwhi le, therefore, t r y i n g t o c l a r i f y the coprecipitation mechanisms t o establish i f and
how i t w i l l be possible t o p r e c i p i t a t e main constituents without contaminants.
Mechanical occlusion o f impurities I s not discussed here because s p e c i f i c predictions, other
than t h a t an increase i n p r e c i p i t a t i o n r a t e w i l l r e s u l t i n an increase i n i r r e g u l a r and
defective c r y s t a l growth, are d i f f i c u l t t o formulate.
3.1 Induced precipitation; post-precipitation
Induced p r e c i p i t a t i o n i s the simultaneous o r nearly simultaneous p r e c i p i t a t i o n o f a t least
two compounds, the more soluble o f which would not have precipitated had the other compound
also not been precipitated. Classical examples are the Induced p r e c i p i t a t i o n o f ammonium
lead sulphate by barium sulphate (ref. 17,18) and o f l i t h i u m by sodium i r o n ( I I 1 ) periodate
(ref. 19).
A form o f induced p r e c i p i t a t i o n can be observed when t r y i n g selectively t o p r e c i p i t a t e
individual major components from a solution o f a complex matrix. I n such cases, the
precipitated compound may cause a simultaneous o r delayed p r e c i p i t a t i o n o f other components.
I f the induced p r e c i p i t a t i o n I s delayed, it i s called mkrum&&&h. For instance, some
metal sulphides are f i r s t precipitated free o f zinc from an acidic solution containing t h i s
element, but zinc i s increasingly precipitated w i t h increasing time o f contact o f the
solution with the p r e c i p i t a t e (ref. 20).
3.2 Adsorption
Adsorption o f trace components i f very Important i n trace analysis, especially a t extremely
low concentrations. Precipitate p a r t i c l e s normally carry a surface e l e c t r i c a l charge because
o f a selective adsorption o f cations o r anions. The charged surface can adsorb, with some
s e l e c t i v i t y , foreign ions o f opposite charge, which also contaminate the p r e c i p i t a t e (ref.
21-24). The extent o f adsorption increases with the charge density on the p r e c i p i t a t e and on
the adsorbing ions. The charge density depends on the available surface area and the
concentration o f primary adsorbing ion. Adsorption on other surfaces may be a source o f
analyte loss i n trace analysis.
I t i s not surprising t h a t the l i t e r a t u r e contains contradictory statements about the e f f e c t
o f p r e c i p i t a t i o n parameters on adsorption. For instance, increasing the temperature i s
reported t o increase (ref. 25) o r decrease (ref. 26,271 the adsorption o f metals ions on
s i l v e r halide and other precipitates. A c i d i t y i s said t o diminish the adsorption o f bismuth
ions (ref. 21,221 on s i l v e r halides o r t o have no observable e f f e c t (ref. 28). Such
apparently c o n f l i c t i n g statements usually arise from the use o f d i f f e r e n t experimental
conditions.

The process o f "adsorption", therefore, i n the context o f p r e c i p i t a t e contamination, I s

complicated, and no clear rules can be established. The Paneth-Fajans-Hahn adsorption rule,
which i s useful as a f i r s t indication o f l i k e l y coprecipitatlon effects, I s not without
exceptions, and cannot be interpreted quantatlvely. Experimental v e r i f i c a t i o n o f such
behaviour o f traces and precipitates therefore remains indispensable f o r r e l i a b l e analytical
application. Two features are clear, however. F i r s t , i f adsorption I s a required p a r t o f
the analytical process, i t i s normally desirable t o achieve the maximum adsorptive surface
area, so t h a t large reactant concentrations should be used during precipitation. Second,
adsorption can occur on a pre-formed p r e c i p i t a t e as well as one formed i n the presence o f the
trace contaminant. Thus, "collection" o f trace components can be achieved by addition o f a
pre-fonned precipitate.
3.3 Bulk coprecipitation (mixed crystal formation)
The basic difference between adsorption and bulk coprecipitation i s t h a t i n the former the
coprecipitated traces are bound t o the surface o f the precipitated p a r t i c l e , whereas i n the
l a t t e r they are d i s t r i b u t e d throughout the p a r t i c l e . Thus adsorbed contaminants can often be
dissolved from the p a r t i c l e surface by appropriate reagents, but those bound w i t h i n the
crystal l a t t i c e are essentially i m b i l i z e d and can only be eliminated by dissolving the
p a r t i c l e (ref. 21).
 Precipitation of major constituents for trace preconcentration 1647

Incorporation o f impurities i n t o the c r y s t a l l a t t i c e implies d i s t o r t i o n o f the l a t t i c e . Thus

the extent o f coprecipitation i s l i k e l y t o be greater, the more e a s i l y the impurity i s
incorporated i n t o the l a t t i c e 1.8. the greater the s i m i l a r i t y i n i o n i c charge and size and
c r y s t a l morphology between the major p r e c i p i t a t e and the coprecipitated species. However,
lack o f s l m i l i a r i t y i n these c r i t e r i a does not exclude the Occurrence o f bulk
coprecipitation, it merely l i m i t s I t s extent. For example, traces o f lead are incorporated
i n t o the s i l v e r chromate l a t t i c e (ref. 29) i n s p i t e o f the f a c t t h a t lead and s i l v e r ions
have d i f f e r e n t charges and lead and s i l v e r chromates have d i f f e r e n t c r y s t a l morphologies.

Bulk coprecipitation i s an important as adsorption for trace analytical purposes because

considerable separation factors can be achieved. The extent o f bulk coprecipitation can be
described mathematically mainly on the basis o f two mechanisms, r e s u l t i n g i n homogeneous and
heterogeneous (logarithmic) d i s t r i b u t i o n . These are b r l e f l y descrtbed below, but have been
discussed i n d e t a i l by Usedowski (ref. 30).
I f a greater Drowrtlan o f the trace impurity i s precipitated than o f the main component,
t h i s i s an "enrichment system", and the r a t i o o f impurity t o main component i n solution
decreases during the p r e c i p i t a t i o n process. As t h i s r a t i o controls the degree o f
coprecipitation, the l a t t e r becomes increasingly small as the p r e c i p l t a t i o n proceeds. I n a
"derichment system", the opposite s i t u a t i o n obtains.
3.3.1 Jj-distributtan. To obtain a homogeneous d i s t r i b u t i o n o f foreign Ions
throughout the l a t t i c e , the p r e c i p i t a t e must be formed very slowly, a t constant temperature
and volume. The e n t i r e s o l i d phase must remain i n thermodynamic equilibrium w i t h the
surrounding solution during the whole o f the c r y s t a l growth process. Thus the speed o f
r e c r y s t a l l i z a t i o n must be a t least as great as the speed o f growth o f the crystals, so t h a t
mixed crystals w i t h a homogeneous d i s t r i b u t i o n o f the trace species are formed, although the
r a t i o s o f main and trace components deposited continually change during the precipitation.
I f these ideal conditions prevail, the concentrations o f the trace (g) and main component (M)
i n the c r y s t a l (c) and the solution (s) a t any stage during the p r e c i p i t a t i o n are as follows
(ref. 31):

_Kt,w i s the separation factor, which remains constant over the e n t i r e course o f the
p r e c i p i t a t i o n f o r which the d i s t r i b u t i o n process i s valid. I n an enrichment system, gt,H i s
> 1, and f o r an appreciable enrichment o f the trace component i n the p r e c i p i t a t e Bt,M > 100.
Fig. 1 shows the relationship between trace and main component concentrations i n the
p r e c i p i t a t e during the p r e c i p i t a t i o n process. I n normal analytical situations i t i s u n l i k e l y
that s u f f i c i e n t t i m e o r experimental control w i l l be available t o ensure t h a t the conditions
allow continuous r e d i s t r i b u t i o n o f an impurity throughout the crystal, even i f i t i s
possible. Thus homogeneous d i s t r i b u t i o n i s l i k e l y t o be rare i n such circumstances.

3.3.2 H e $ x ~ l n ~ , d i & & W Such. a d i s t r i b u t i o n i s obtained when no

internal reorganization o f the c r y s t a l l a t t i c e occurs during c r y s t a l growth. Thus each layer
o f crystal i s i n equilibrium with the solution present a t the t i m e i t i s l a i d down. As the
solution composition and, especially, the trace:main component r a t i o , continually change
during precipitation, the d i s t r i b u t i o n o f the trace impurity throughout the c r y s t a l i s not
homogeneous, but logarithmic (ref. 32).

where It_] and [El are as above, i n i t i a l l y (1) or a f t e r p r e c i p i t a t i o n has continued f o r time
;, and X i s the logarithmic d i s t r i b u t i o n coefficient. Again, f o r trace enrichment, L > 100 i s
desirable (Fig. 1). Fig. 1 also shows t h a t a greater separation i s achieved f o r a given
d i s t r i b u t i o n coefficient, when logarithmic rather than homogeneous d i s t r i b u t i o n i s achieved.

Fig. 1 . Dependence of proportion of impurity

precipitated with proportion of carrier
precipitated for homogeneous and heterogeneous
coprecipitation.

Carrier precipi t nted (%I

1648 COMMISSION ON MICROCHEMICAL TECHNIQUES AND TRACE ANALYSIS

Logarithmic d i s t r i b u t i o n i s more c0rmK)n than homogeneous d i s t r i b u t i o n (ref. 18); normally,

however, incomplete r e d i s t r i b u t i o n o f impurity w i t h i n the c r y s t a l occurs, so t h a t an
intermediate d i s t r i b u t i o n equation w i l l hold.
3.3.3 LffiacJ; o f m & l Q i ~ ~ , Both e . d i s t r i b u t i o n equations assume equilibrium
conditions, e i t h e r a t the crystal/solution interface, or, more rarely, throughout the
complete solution/crystal system. Under analytical conditions, the rate o f p r e c i p i t a t i o n i s
l i k e l y t o be too f a s t t o allow such e q u i l i b r i a t o be established. Several investigators have
shown t h a t A i s a function o f p r e c i p i t a t i o n rate (ref. 16,33,34), and t h a t X ->1 as the rate
increases i.e. the process becanes less discriminating.

For the most e f f e c t i v e analytical separations t o be based on bulk coprecipitation, therefore,

i t i s necessary t o ensure t h a t the value o f 1 - 1 s as d i f f e r e n t from u n i t y as i s feasible, by
carrying out the p r e c i p i t a t i o n slowly. Precipitation form homogeneous solution has been
shown t o provide a very e f f e c t i v e control o f the p r e c i p i t a t i o n rate (ref. 15,35,36).
3.4 Conclusions
here i s s t i l l much t o be learnt about the mechanisms o f trace coprecipitation. Effects l i k e
adsorption o r formation o f mixed crystals are d i f f i c u l t t o elucidate, so t h a t i t i s usually
impossible t o predict accurately the behaviour o f trace components i n the presence o f
precipitates. Behaviour must be established experimentally, f o r each set o f experiment
conditions, but i t must be emphasized t h a t it i s unreliable t o extrapolate behaviour under
such a set o f conditions t o other circumstances. Frequently It I s necessary t o control the
r e l i a b i l i t y o f procedures based on matrix p r e c i p i t a t i o n by means o f independent methods o f
separation and determination o r by analysis o f reference materials.

4. APPLICATIONS OF MATRIX PRECIPITATION IN TRACE ANALYSIS

The choice o f a separation and preconcentratlon method i n trace analysis depends on numerous
well-documented considerations. These include the following, which increase i n importance
the smaller the trace concentration.
4.1 Blank problems
I n general, procedures have t o be favoured which allow the use o f the minimum amounts o f
reagents which can be p u r i f i e d i n a simple way (ref. 37). The use o f large amounts o f
reagents generally causes high and often variable blank values resulting i n an increase o f
the lower detection l i m i t . Thus, the improvement i n detection l i m i t s obtained by the use o f
a preconcentration procedure may be p a r t l y o r completely counteracted by an increase i n blank
scatter. Frequently, procedures f o r separating major components w i l l need larger amounts o f
reagents than those f o r traces, and buffer solutions and complexing agents f o r the matrix
components may be required. Additionally, during trace analysis, the necessary transfer o f
the matrix i n t o a rather large volume o f a second phase o r the concentrating o f the resulting
matrix-free solution i s often accompanied by high blanks.
The "cementation" o f m e t a l l i c main components by reduction with metals o f very low redox
potentials i s s i m i l a r t o the use o f normal precipitants. This method, however, often cannot
be reconnmnded f o r trace analysis because o f the high blank values t o be expected because i n
addition t o the ions o f the reducing metal (e.9. A l , Hg, Zn), ions o f impurities i n these
metals also dissolve.
4.2 Interactive effects
When separating matrix components, the p a r t i t i o n behaviour o f trace species depends on the
composition and concentration o f the sample solution, as described above. Often during
evaporation, extraction, p r e c i p i t a t i o n o r chromatography o f real samples, trace
concentrations are decreased, sometimes t o zero. Such e f f e c t s are usually d i f f i c u l t t o
control, and extended experimental work i s required t o achieve some understanding o f them.
The influence o f such e f f e c t s on the analytical results can best be established by analyzing
reference materials o r by comparing the results with those o f independent reference
procedures.
4.3 Universality
I n general the efficiency o f procedures i n which matrix components are precipitated i n order
t o concentrate traces strongly depends on s t r i n g e n t l y following the established, optimized
procedures. Changes i n sample solution volume, reagent concentrations, reaction time,
temperature etc. may a f f e c t the e f f i c i e n c y o f the separation.
I n s p i t e o f the many problems, procedures are nevertheless often applied i n which the major
components are separated from trace analytes and removed. This i s usually necessary because
c e r t a i n matrix elements react undesirably with most o f the c0rmK)n chelating agents.
Therefore i t I s extremely d i f f i c u l t t o f i n d suitable conditions which allow freedom o f
interference f o r separation o f trace analytes from, f o r example, a large excess o f matrix
components such as Ag+, Cup+, Hg2+, Pb2+ o r Bis+. I n such cases it i s more productive t o t r y
 Precipitation of major constituents for trace preconcentration 1649

t o f i n d a means o f selectively p r e c i p i t a t i n g the matrix. Such p r e c i p i t a t i o n i s mostly

brought about with simple precipitants; chelating agents, i n general, are too expensive t o
be used f o r p r e c i p i t a t i n g main components.
Such precipitations have some advantages. They can r e l a t i v e l y e a s i l y be carried out by
trained technicians i n a normal wet chemistry laboratory, provided t h a t the basic
requirements o f trace analysis and the demands for clean working conditions are met. This
s i m p l i c i t y o f execution, however, should not obscure the complicated mechanisms which cause
every new application t o become an adventure which may be r i c h i n surprises!

5. GUIDELINE FOR AVOIDING SORPTION LOSSES

Below, some guidelines are formulated which, during the development and application o f
preconcentration techniques by p r e c i p i t a t i o n o f the matrix, may be useful f o r avoiding losses
o f traces by sorption. Such guidelines are already known from gravimetry; they originate
from general analytical experience o f the sorption behaviour o f trace elements onto freshly
precipitated materials.

.GuU.alb~A: Select the conditions f o r a matrix p r e c i p i t a t e t o ensure t h a t p a r t i c l e s with

the smallest possible s p e c i f i c surface are obtained.
pUide.LLnS_P: Select the conditions f o r a matrix p r e c i p i t a t i o n so t h a t the trace components
o f interest would not p r e c i p i t a t e i f present i n a much larger concentration o r i f present
alone i n the sample solution.
SiUFdallnU: Do not p r e c i p i t a t e the matrix quantitatively i f an excess o f the precipitant
causes sorption o f the trace components o f interest.
liui-4: Convert trace ions which are l i k e l y t o be sorbed onto the p r e c i p i t a t e i n t o
complexes which w i l l not be sorbed.
Additionally, i t should be borne i n mind t h a t the p r e c i p i t a t i o n behaviour o f trace
concentrations o f almost insoluble compounds cannot be deduced from t h e i r s o l u b i l i t y
products. Finally, v o l a t i l e reagents t h a t can be p u r i f i e d easily,e.g. by isothermal
d i s t i l l a t i o n , Should be used as precipitants. I n t h i s way the blanks are kept low and trace
concentrates can be obtained by evaporation o f the precipitant under "clean" conditions (ref. 37).

6. EXAMPLES TO ILLUSTRATE THE GUIDELINES

The application o f the guidlines i n Section 5 are i l l u s t r a t e d below with some examples o f
multi-element preconcentration. Only the principles and the results o f the matrix separation
methods are described. The detailed analytical procedures should be sought i n the o r i g i n a l
l i t e r a t u r e (Section 7).
6.1 Precipitates with small specific surfaces
There i s a d i r e c t correlation between the size o f p a r t i c l e s and the p u r i t y o f a p r e c i p i t a t e
(Section 2.3). Therefore i t i s often better t o p r e c i p i t a t e a matrix component as a compound
o f greater s o l u b i l i t y , and usually o f greater p a r t i c l e size, than t o select ony sparingly
soluble precipitates. Also, the p r e c i p i t a t i o n process should be controlled i n such a way
t h a t the formation o f nuclei and c r y s t a l growth proceed s u f f i c i e n t l y slowly t o t h a t the
p r e c i p i t a t e obtained has large p a r t i c l e s and i s as pure as possible. Traces, however, may be
l o s t by mixed c r y s t a l formation, even under these optimal conditions.
Exrunela: Precipitation o f the matrix ions M2+ (H = Pb, Sr, Ba) as H(NO312.
A t y p i c a l example o f the preconcentration o f numerous elements according t o Guideline 1 i s a
method described by Ustimov &A. i n which lead as a matrix element i s precipitated as lead
n i t r a t e (ref. 38,39). The procedure I s based on the f a c t t h a t the high s o l u b i l i t y o f lead
n i t r a t e i n water (0.52 g m l - l ) decreases i n 85% n i t r i c acid t o a value which i s lower, f o r
example, than t h a t o f lead chloride i n water (ref. 40). The sample o f lead metal (e.g. 10 g)
I s dissolved i n (1+1) n i t r i c acid. On evaporation o f water, the n i t r i c acid concentration
increases and the s o l u b i l i t y o f lead n i t r a t e decreases simultaneously i n a nearly l i n e a r
fashion. When p r e c i p i t a t i o n s t a r t s the s o l u b i l i t y i f s t i l l r e l a t i v e l y large, so well-formed,
highly pure crystals o f a few mm diameter are slowly formed.
Two processes control the p r e c i p i t a t i o n rate, the decrease i n the solution volume and the
increase o f the n i t r i c acid concentration. Precipitation stops when t h e n i t r i c acid-water
azetrope (ra. 65% HNOs) i s obtained. Only 30 mg o f lead remains dissolved i n 100 cms o f t h i s
acid mixture, but >95% o f the following elements remain i n the solution: Ag, A l , B i , Cd, Co,
Cu, Fe, Ga, In, K, Mg, Na, N i , Pd, T1 and Zn. These elements can be separated from the lead
matrix simply by decantation from the precipitated lead n i t r a t e ; t h e i r concentration may be
increased by further evaporation o f the solution.
Lead chloride and sulphate precipitated under the same circumstances would coprecipitate
larger proportions o f the trace Components than lead n i t r a t e . Because other separation
methods (e.g. extraction, evaporation, chromatography) can hardly be applied t o the lead
matrix, p r e c i p i t a t i o n as lead n i t r a t e i s probably the best procedure f o r multi-element trace
concentration from lead and i t s compounds.
1650 COMMISSION ON MICROCHEMICAL TECHNIQUES AND TRACE ANALYSIS

M more than 30 metal n i t r a t e s only strontium and barium n i t r a t e s show s i m i l a r s o l u b i l i t y

behavlour i n n i t r i c acid t o lead n i t r a t e (ref. 41). A l l the other n i t r a t e s are much more
soluble i n n i t r i c acid than i n water, because o f n i t r a t e complex formation. Traces o f
strontium and barium are coprecipltated completely with lead n i t r a t e , because the n i t r a t e s o f
these elements have the same type o f c r y s t a l l a t t i c e (T%) and the l a t t i c e constants are
similar. Likewise strontium and barium as main components can be separated as n i t r a t e s from
numerous elements (ref. 411, but not from lead.
A s i m i l a r technique, i n which the s o l u b i l i t y o f a compound decreases upon change i n
composition o f a solvent, i s the p r e c i p i t a t i o n o f matrix aluminium as AlCls.6HzO by
introducing hydrogen chloride gas i n t o a water/diethyl ether mixture (ref. 42-45). Alkali
and alkaline earth metals and magnesium as major components can also be separated i n a
s i m i l a r manner (ref. 46).
6.2 Prevention of trace precipitation
To minimize copreclpltation, the p r e c i p i t a t i o n conditions f o r the matrix should be chosen so
that even much higher concentrations o f the trace analytes would not p r e c i p i t a t e i f they were
alone i n solution. This means, f o r example, t h a t the pH o f the sample solution should be
such t h a t only the major component reacts s i g n i f i c a n t l y w i t h the precipitant, and the trace
species remain i n solution. Similar discrimination can be achieved by addition o f a u x i l i a r y
complexing agents, redox agents etc. (ref. 47).
The search f o r the most appropriate conditions f o r p r e c i p i t a t i o n i s d i f f i c u l t because the
range o f conditions i n which p r e c i p i t a t i o n occurs depends on d i f f e r e n t parameters, such as
the concentration o f the main components and the temperature. The i n i t i a l t u r b i d i t y , f o r
example, i n the p r e c i p i t a t i o n o f zinc hydroxide occurs a t a pH lower by 4 f o r 100 mg Zn2+ cm-
3 than f o r 100 pg Zn2+ I f a precipitant forms stable, soluble complexes with the trace
analytes but not with the matrix species, coprecipitation can be avoided by the use o f a
large excess o f the reagent. Thus i n the p r e c i p i t a t i o n o f matrix i r o n ( I I 1 ) with anmonia,
traces o f Ag, Cd, Co, Cu, N i and Zn remain i n solution as m i n e s .

Exampla: Precipitation o f matrix copper(I1) ions as copper(I1) sulphide.

There are many reasons why metal sulphide precipitations are not very suitable f o r matrix
separations. Hydrogen sulphide i s a p a r t i c u l a r l y unselective precipitant, so t h a t many trace
metals are coprecipitated. Additionally metal sulphides have p a r t i c u l a r l y low solubi 1i t i e s .
The addition o f hydrogen sulphide often produces precipitates o f i l l - d e f i n e d composition,
with large amounts o f c o l l o i d a l p a r t i c l e s o f large surface area. This r e s u l t s i n very strong
sorption o f cations and anions. Furthennore the low s o l u b i l i t i e s make i t d i f f i c u l t t o
increase the s e l e c t i v i t y o f the p r e c i p i t a t i o n reaction by adding a u x i l i a r y reagents. It i s
not surprising, therefore, t h a t sulphides are more usually used as v e r s a t i l e c o l l e c t o r
precipitates. The number o f elements which can be precipitated decreases as the a c i d i t y o f a
solution i s increased. This i s also t r u e f o r the number o f elements which coprecipitate with
a metal sulphide,and f o r the amounts coprecipitated.

To separate copper without loss o f trace analytes from the solution, Quideline 2 indicates
t h a t the a c i d i t y of the sample solution should be adjusted w i t h hydrochloric acid so t h a t
j u s t s u f f i c i e n t copper i s precipitated, but traces o f elements having larger s o l u b i l i t y
products remain mostly i n solution. The e f f e c t o f a c i d i t y upon preconcentratlon e f f i c i e n c y
f o r several metal ions i n the Ng g-’ range i s given I n Fig. 2. The amount o f separated
matrix i s 1 g o f copper. According t o Fig. 2, the trace elements behave only approximately
i n the way t h a t would be expected from t h e i r s o l u b i l i t y products.

To separate the matrix copper as a p r e c i p i t a t e with the smallest possible s p e c i f i c surface

area and t o obtain a solution t h a t contains the trace analyte which i s as free as possible o f
residual matrix, the following conditions f o r p r e c i p i t a t i o n were chosen:
-- The precipitant (HS-1 I s formed i n homogeneous solution by hydrolysis o f thioacetamide.
The matrix copper i s precipitated from b o i l i n g solution.
- Precipitate and mother l i q u o r are separated Inmediately a f t e r precipitatlon.
- The f i l t r a t e i s a c i d i f i e d with n i t r i c acid t o remove the excess o f thioacetamide and i t s
hydro1y s i s products during the evaporat 1on process.
I f 1 g o f copper i s precipitated i n t h i s way as copper(I1) sulphide from 3M hydrochloric
acid, the recovery from the f i l t r a t e o f 1-50 c(g o f Cd, Co, Fe, In, Hn, N i , Pb and Zn i s
> 90%. Traces o f elements which form sulphides less soluble than copper(I1) sulphide
coprecipitate nearly completely with the matrix (ref. 48).
6.3 Incomplete matrix precipitation
From the s t a r t o f p r e c i p i t a t i o n t h r w h g the equivalence point t o when an excess o f
precipitant i s present, the location o f the trace species may change several times between
solution and precipitate. Complicated sorption curves are obtained especially i f major
components are precipitated as almost insoluble i o n i c compounds which aquire an e l e c t r i c a l l y
charged surface by adsorption. As discussed i n Section 3.2 t h i s charge leads t o the
 Precipitation of major constituents for trace preconcentration 1651

100
'00 =m:-eT:

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2 60 i-
23C 80
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;
I: ;s
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HCI conc.(MI
F i g . 2. E f f e c t o f a c i d i i y on t h e s o r p t i o n
o f trace metal ions M" on C ~ S .

adsorption o f foreign ions from t h e sample solution. Precipitates bearing a p o s i t i v e charge

due t o adsorption o f t h e i r c m n cations have a tendency f o r "secondary adsorption" o f
foreign anions, and vice versa. A t the isoelectronic point losses o f traces o f cations o r
anions by e l e c t r o s t a t i c adsorption are not t o be expected. This i s o e l e c t r i c point, however,
I s d i f f i c u l t t o achieve experimentally, because it does not always coincide with the
equivalence point o f a p r e c i p i t a t i o n process. Additionally, other sorption processes whlch
are not controlled by e l e c t r i c a l charge may occur even a t the i s o e l e c t r l c point.
Effects s i m i l a r t o a charge-controlled sorption process also occur when trace elements and
matrix react with a precipitant, with the trace compounds formed being more soluble than t h a t
w i t h the matrix. Whi 1st some matrix remains unprecipitated t h i s prevents the p r e c i p i t a t i o n
o f the trace compounds, almost u n t i l the equivalence point is reached. Only a f t e r t h i s
stage, upon addition o f f u r t h e r precipitant, are the trace compounds precipitated together
with the small amount o f residual matrix. So, very often It I s not possible t o distinguish
whether coprecipitation o f c e r t a i n elements i s caused by adsorption, depending on the
e l e c t r i c a l charge o f the precipitate, o r by the s i m i l a r s o l u b i l i t i e s o f matrix and trace
compounds. I n many cases both mechanisms may be involved simultaneously (ref. 28).
Therefore, i n such circumstances, i n order t o concentrate large numbers o f trace species with
recoveries as high as possible, a p a r t i a l p r e c i p i t a t i o n o f the matrix should be attempted
(Guideline 3 ) . The matrix which remains i n the f i l t r a t e may be eliminated without
significant loss o f the trace elements by a second, s i m i l a r p r e c i p i t a t i o n step.

Examole: Precipitation o f matrix s i l v e r as s i l v e r chloride.

There are several important reasons i n trace analysis why hydrochloric acid i s well suited
f o r the p r e c i p i t a t i o n of s i l v e r . I t can be p u r i f i e d e a s i l y by isothermal d i s t i l l a t i o n .
S i l v e r chloride i s e a s i l y f i l t e r e d , and is s u f f i c i e n t l y insoluble t o allow a quantitative
separation o f the matrix s i l v e r yielding, upon concentration o f the f i l t r a t e , a trace
concentrate which I s nearly free o f matrix. There are only a few other s l i g h t l y soluble
metal chlorides, so it i s possible t o p r e c i p i t a t e the matrix with high s e l e c t i v i t y . Because
of the surface charge on the precipitate, It is unavoidable t h a t traces coprecipitate t o
d i f f e r e n t extents upon addition o f an excess of precipitant (ref. 24). Bismuth, Cd2+, Hg2+,
Pb2+, Pdzt, T1+ and T l I I I , especially, coprecipitate i n t h i s way, whereas Ce3+, Co2+, C r s + ,
Cu2+, Fest, Gas+, In3+, La3+, Mn2+, Ni2+, RhIII, SnIv, Th4+, U022+ and Zn2* remain nearly
quantitatively i n solution.

The adsorption process i s largely reversible with respect t o a change o f the e l e c t r i c a l

charge; it depends l i t t l e on the a c i d i t y o f the solution, and the fractions o f adsorbed
traces decrease as the temperature increases. As an example o f the behaviour o f trace
elements which can be adsorbed by s i l v e r chloride, Fig. 3 shows the extent o f adsorption o f
traces o f lead. I t begins j u s t before the equivalence point, a t room temperature o r near the
b o i l i n g point o f water. The equivalence point I s marked by the v e r t i c a l dotted l i n e . Such
diagrams suggest a way o f avoiding coprecipitation losses. Most the trace elements which
normally are sorbed remain i n solution i f only about 90% o f the s i l v e r is precipitated, a t a
temperature near the b o i l i n g point. I f the subsequent trace determination I s l i k e l y t o be
affected by the s i l v e r remaining i n solution a f t e r the f i l t r a t i o n o f the s i l v e r chloride,
t h i s residual s i l v e r may be precipitated almost quantitatively i n a second, s i m i l a r 90%
p r e c i p i t a t i o n step without substantial sorption o f the trace species. High recoveries of
many trace species are obtained by t h i s two-step matrix p r e c i p i t a t i o n (ref. 49).
1652 COMMISSION ON MICROCHEMICAL TECHNIQUES AND TRACE ANALYSIS

6.4 Formation of non-adsorbable complexes

As has been described, coprecipitation of some trace elements onto hydrated i r o n ( I I 1 ) oxide
can be prevented by formation of m i n e complexes. I f charge-controlled adsorption o f
cations i s the reason f o r losses during the enrichment process, o r i f cations are l o s t by
formation o f mixed crystals, i t may be possible t o increase the recovery by complexation o f
the traces t o be enriched. This has been studied i n d e t a i l f o r precipitates o f s i l v e r and
thallium(1) halides (ref. 28,501.
The proposed complexation technique i s e f f e c t i v e especially i f adsorbable trace cations are
converted i n t o complex anions. I n such cases, by using an anionic precipitant i n excess ,
the sign o f the charge on the p r e c i p i t a t e and the trace complexes are the same and adsorption
i s prohibited. I n some cases, however, i t i s found t h a t a few elements which previously were
not sorbed as cations now are coprecipltated as complex anions. Fortunately t h i s phenomenon
only occurs during t h a t p a r t o f the p r e c i p i t a t i o n process when the matrix has not been
separated completely (ref. 28). Provided t h a t such premature adsorption processes are
s u f f i c i e n t l y reversible, the sorbed trace complexes dissolve again when the equivalence point
o f the p r e c i p i t a t i o n reaction i s passed. O f course, success i n preventing trace losses is
achieved only ifcomplexing agents are used which preferably react with the traces whereas
the matrix element remains essentially unaffected.

E&,-,,~Q: Precipitation o f matrix thallium as thallium(1) iodide i n the presence o f EDTA.

Compared with the s i l v e r halides, thallium(1) halides aquire less charge by adsorption o f
t h e i r common ions. Accordingly the number o f adsorbable metal cations, and t h e i r adsorption
rates, are less than f o r s i l v e r halides. For the separation o f matrix thallium,
p r e c i p i t a t i o n o f thallium iodide may be used because o f i t s low s o l u b i l i t y . S e l e c t i v i t y ,
however, i s not very high because traces o f B i , Cd, Cu, Pb, Ag, Au, Pd and P t are removed by
the p r e c i p i t a t e i n the separation process. Noble metals and s i l v e r are sorbed i r r e v e r s i b l y ,
possible a f t e r reduction, whereas the other ions mentioned are sorbed by a reversible charge-
controlled process. A t higher concencentrations, the formation o f s l i g h t l y soluble iodides
should also be considered.

EDTA i s very suitable f o r conversion o f B i 3 * , Cd2+, Cu2* and Pb2+ t o anionic complexes.
Chelates o f the doubly and t r i p l y charged trace cations have pK ( s t a b i l i t y constant) values
between 16 and 28 and therefore they are f a r more stable than the thallium(1)-EDTA complex
(PK = 5.8). This enables p r a c t i c a l l y complete complexation o f the traces by using only a
small concentration o f EDTA; a lO*-fold excess o f thallium(1) does not interfere.
Obviously, with regards t o the pH s e n s i t i v i t y o f the pK values, the p r e c i p i t a t i o n should be
carried out i n a nearly neutral solution. Instead o f hydriodic acid an a l k a l i metal iodide
should therefore be used, which i n t u r n i s the reason why the r e s u l t i n g f i l t r a t e cannot be
concentrated without producing residues o f a l k a l i metal salts.
The influence o f EDTA on the sorption behaviour o f trace species i s shown i n Fig. 4 f o r
bismuth. This cation is l o s t completely a f t e r addition o f an excess o f precipitant, whereas,
the anionic EDTA chelate o f bismuth remains quantitatively i n solution. Other cations
capable o f sorption behave i n the same way. This technique thus allows the following
elements t o be separated from matrix thallium with recoveries >95X: A l l B i , Cd, Co, Cu, Fe,
Gal In, La, Mg, Mn, N i , Pb, Sn, Th, U and Zn. The noble metals are l o s t even i n the presence
o f EDTA (ref. 50).

Fig. 4 . E f f e c t o f NaI c o n c e n t r a t i o n on +
t h e a d s o r p t i o n of t r a c e B i 3 ' on 2 g T1
p r e c i p i t a t e d a s T1I: ( a ) B i 3 + c a t i o n s ;
(b) Bi3+-EDTA a n i o n s .

NaI cant (mM1

7. TABULATION OF PROCEDURES I N V O L V I N G M A T R I X PRECIPITATION

The publications given i n Table I concerning matrix p r e c i p i t a t i o n f o r multi-element
preconcentration from pure metals have been obtained mostly from Analytical Abstracts and the
abstracts i n Fresenius Zeischrift f u r Analytfsche Cheunie. I n most o f them the quoted
preconcentration method i s combined with a spectrochemical o r radiochemical measurement step.
 Precipitation of major constituents for trace preconcentration 1653

The lack o f d e t a i l s i n these abstracts r e s t r i c t s the s pec i f i c at i on o f data about the

procedures (recoveries, precision, accuracy etc). So, f o r application o f any o f the quoted
methods, consultation o f the o r i g i n a l papers i s reccimmnded.

TABLE I. Matrix p r e c i p i t a t i o n f o r multielement preconcentration. (el) = electrolytic

deposition.

Matrix Element Precipitated Fonn Preconcentrated Trace Element Reference

Ag As, Cd, Cu, Fe, GA, I n, Hn, 51

Ni, Pb, T1, Zn
Ag ( e l ) Au, Co, Mn, Ni, Sb, Sn 52
AgCl Cd, Co, Cu, N1, Zn 53
AgCl Cd, Cu, Fe, Mn, N i , Pb, Zn 21
AgCl Bi, Cu, I n, Pb, Sb, Zn 54
AgCl Co, Cr, Fe, Mn, Ni 55
AgCl Al, Au, Ca, CO, CU, Fe, Hg, 56
Ir, Mg, Mn, Ni, Os, Pd, Pt,
Rh, Ru
AgCl As, Au, Cu, Sb 57
A1 AlCls.6HzO Ag, B i , Cd, C r , Cu, N i , Pb, 43
Zn
A l C l s .6HzO Cu, Fe, Mg, Mn, S i , T i 44
AlC13.6HzO C r , Cu, Fe, Ga, Mg, Mn, N1, 45
V, Zn

Au Au "numerous elements" 58
Au 26 elements 59
Au ( e l ) As, P, S i 60
Bi 81Is A l , Ba, Ca, Cd, Co, C r , Fe, 61
In , Mg, Hn, Ho, N i , Te, T i ,
V, Zn
BiOBr A l , Ca, Cd, Co, Cu, Fe, Ga, 62
In, Mg, Mn, N i , T1, Zn
B i ON03 Ag, A l , Cd, Cu, Mg, Mn, N i , 63
Pb

Cd Cd ( e l ) Co, Mn, N i , Zn 64

cu cu ( e l ) Bi, Pb, Sn 65
cu ( e l ) Fe, Mn, N i , Sb, Sn, Zn 66
cu ( e l ) Ag, As, Au, Cd, Co, C r , Cs, 67
Fe, Ga, Hf, Hg, I n, La, Mn,
Mo, Ni, P, Rare Earth Metals,
Rb, S, Sb, Sc, Se, Te, Th, U, Zn
cu ( e l ) Ag, A l , Au, Ba, Bi, Ca, Cd, 68
Co, C r , Fe, Mg, Mn, Mo, N i ,
Pb, Pt, Sb, Sn, T i , V, Zn
cus Cd, Co, Fe, I n , Mn, NI, Pb, 48
T1, Zn

Geoz As, Au, Cd, Cu, Hg, Sb, Zn 69

GeO2 Ag, As, Au, Cd, Co, Cu, Fe, 10
Ga, Hg, I n , Pb, Re, Zn

A l k a l i Metals, Alkaline 71
Earth Metals, A l , As, Be,
B i , Cd, Cr, Co, Cu, Fe, Ga,
In , Mg, Mn, N i , Pb, Sb, Sn,
Te, T i , T1, Zn

Mo no-a-benzoin Ag, A l , Ba, B i , Ca, Cd, Co, 72

Cr, Cu, Fe, I n, Mg, Mn, N i ,
Pb, Sb, Sn, T I , V, Zn

0s 0s Au, Fe, Ir, Pd, Pt 73

1654 COMMISSION ON MICROCHEMICAL TECHNIQUES AND TRACE ANALYSIS

~~

Matrix Element Precipitated Fona Preconcentrated Trace Element Reference

Pb Pb(N0a 12 Ag, A l , As, B i , Ca, Cd, Co, 38

Cu, Fe, I n , Mg, Na, N i , Sb,
T1, Zn
Pb(N0a 12 Ag, Al,'As, B1, Ca, Cd, CO, 39
Cu, Fe, Ga, In, Mg, Na, N i ,
Sb, T1, Zn
Pb(N0s 12 Ag, A l , Bi, Cd, Co, Cu, Fe, 40
Oa, Hg, In, K, Mg, Mn, Na,
NI, Pd, T1, Zn
PbCln Ag, A l , As, Au, B, Ba, Be, 74
Bi, CA, Cd, Co, C r , Cu, Fe,
Ga, In, K, La, Mg, Mn, Mo,
Na, N i , P, Pd, Pt, Sb, S i ,
Sn, Sr, T1, U, Zn
Ag, A l , Au, B i , Cd, Co, Cu 40
Fe, Ga, In, K, Mg, Mn, Na,
Ni, Pd, Sb, T1, Zn
PbSOi Cd, Zn 75
PbSO4 Ag, As, B i , Cu, Fe, Mg, Sb, 76
Sn, Zn
Cd, Cu, Zn 77
Cd, Co, Cu, Fe, Qa, I n , Zn 78
Ag, Al, As, B i , Ca, Cd, Co, 47
Cr, Cu, Fe, In, Mg, Hn, Mo,
Na, N i , Sb, Sn, Te, T i , V,
Zn
Al, B i , Ca, Cd, Co, Cu, Fe, 40
Ga, Hg, I n , Mg, Mn, Na, N i ,
Pd, Sb, Zn

Pd Pd Cd, Co, Fe, Hg, Ru, Zn 79

Pd-diwthyl- Co, Fe 73
g1yoxi me
Pd-d imthy 1 - " impur it ies" 80
glyoxime

Pt Pt Cu, Fe, N i , Pb, Te 81

Pt Ag, Cd, CO, Fe, Hg, Ru, Zn 82
Pt ( e l ) As, P, S i 60
(NH4)nPtCls As, Sb 83
(NH4)aPtCls Se, Te 84
(NH4)~Ptclr impurit ies" 80
(NH4 12 P t C l 6 Ag, 81, P, Sb 85

Se Se As, Cu, Fe, Zn 86

se As, Cu, Sb, Te 87
Se As, Cd, Cu, Fe, Ga, Hg, In, 88
Sb, Te, T1
Se AS, CU, Sb, Te 89
Se Mo, P, S, W, Zn 90

Te Te Al, AS, BI, Cd, CO, C r , CU, 91

Fe, Ga, In, Mg, Mn, Mo, N i ,
Pb, Sb, Sn, T i , T1, V, W, Zn
Te As, Cu, Sb, Se 89
Te Mo, P, S, W, Zn 90
Te Cd, Zn 92
TeO2 Ag, Al, AS, Au, B i , Ca, 93
Cd, Co, C r , Cu, Fe, In, Mg,
Mn, Na, N i , Pb, Sb, S1, Sn,
T1, Zn
TeOr Co, N1 94
TeOr Cd, Cu, Zn 84

Th Th-oxalate Ag, A l , Ba, Ca, Cd, CO, C r , 95

Cu, Fe, Mg, Mn, Mo, N1, Sb,
Sn, T i , V, Zn
Th-h ydrogen perox ide Ag, A l , Ba, Ca, Cd, Co, Cr, 95
Cu, Fe, Mg, Mn, Mo, N i , Pb,
Zn

Zr Zr-mandel i c a c i d " impur 1t ies" 96

 Precipitation of major constituents for trace preconcentration 1655

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