8. W.
Smith
and M. L. Parsons1
Preparation of Standard Solutions
Arizona State University
Tempe, 8.5281 Critically selected compounds
It is often necessary in chemical analysis, especially
trace elemental analysis by flame spectrometric methods,
molecular absorption techniques, etc., to prepare solutions
containing known concentrations of given elements. In
many cases it is difficult to make a choice as to what
compound is best suited for these solutions. No complete.
. .
up-to-date tabulation of well-suited compounds has been
found in the literature. General textbooks of analytical
chemistry occasionally give lists of primary or secondary
standards often used in acid-base and oxidation-reduction
titrations, hut do not discuss the preparation of solutions
for flame analysis. A few references are available (I, 2)
which give details for preparing a great many chemical
reagents, both organic and inorganic. One of these (1)
contains a brief listing of how to prepare solutions for
some 29 elements. It is felt that a more complete listing of
good choices of compounds to be used for preparing solu-
tions of the elements would he useful not only to the prac-
ticing analytical chemist hut also to those engaged in
basic flame research.
As a basis for making the selections of compounds suit-
able for use in preparing standard solutions of the ele-
ments, the following criteria were followed
Stability
I ) The compound shauld not he deliquescent, efflorescent, or
hygroscopic.
2) The compound should not undergo a change upon drying.
3) The compound should be easily weighable.
4) Bath the solution and the eampound from which it is pre-
pared should be stable
purity
1) The compound should be available to a purity of 99.5% or
better.
Ease of Preparation
1) The compound should be soluble in water, common acids or
hases.
2) The compound should be easy to handle.
Auoilnbility
1) The compound should be readily available from common
chemical suppliers.
2) The compound should not be unnecessarily costly.
High Molecular Weight
1) The compound should have as high a molecular weight as
possihle for accurate weighing.
Toxicity
1) The compound should have as low a toxicity as possihle.
Of course, very few of the chemical compounds examined
conformed to these criteria completely. Those few that do
are the well known "Primary Standards." These have
been noted in the accompanying tahle. When examining
the possibilities for a given compound the criteria were
considered in the order listed. Some of the choices are less
than ideal, h u t it is felt that the compounds listed are the
best possihle and that with careful preparation, solutions
made from these will he of accurate concentration.
Several sources were consulted in making the initial list
of possihle com~ounds.The "Merck Index" (3) . . and the
andho hook of Chemistry and Physics" (4) were first
'To whom all correspondence should he addressed.
searched, one element a t a time, and the likely candidates
were listed with their properties. These lists generally in-
cluded the common salts (sulfates, halides, nitrates, and
carbonates), the oxides, and the elements themselves.
Compounds containing the element as the anion and the
cation were both considered, when possible. Where further
details concerning the physical properties were required,
more complete references were consulted (5-9). The crite-
ria were then applied in detail to arrive a t a maximum of
three choices. With the exception of hafnium and zirconi-
um, samples of these compounds were then ohtained and
examined in the laboratory. Solubility data were checked
qualitatively, and compounds were checked for hygroscop-
icity, deliquescense, and efflorescense. In some cases,
compounds which were noted as being slightly efflorescent
or deliquescent in the literature were found to he suitable
for accurate weighing. These were checked by placing a
small sample (ahout 1 g) of the compound on a n analyti-
cal balance and recording its weight a t periodic intervals
for up to 3 hr. Compounds whose weights changed by
more than 2 mg (two parts in a thousand) were rejected.
It should he noted that the humidity in our laboratory is
probably lower than that in many parts of the United
States. Once the final choices had been made, 1000 ppm
solutions were prepared of all of the elements in the tahle
except for europium, terbium, zirconium, thulium, rheu-
ium, iridium, scandium, hafnium, rhodium, lutetium, os-
mium, and ruthenium. Solutions of these twelve elements
were not prepared due to high cost and, in the case of os-
mium, extreme toxicity.
Several chemical suppliers in the United States produce
"standard" solutions of the elements for use in atomic ah-
sorption analysis. As possihle support for our final choices,
data sheets showing the composition of these solutions
were ohtained from five different companies. In only a few
cases did our choices coincide with these. In general, the
commercially availahle standards were prepared with em-
phasis on water solubility. Two firms used water soluble
compounds in all solutions, many of which were highly
hygroscopic or even liquid. This would indicate that these
solutions are prepared by approximate weighing followed
by standardization by atomic absorption spectrometry or
other suitable techniques. In the authors' opinion, the
preparation of standard solutions by accurate weighing of
a compound of known composition is a more satisfactory
approach. Whereas weighing may he done to a t least
*0.01% precision and dilution to about 0.190,a standard-
ization technique using, for instance, atomic absorption
spectrometry will give a precision of only about +I%. The
compounds chosen in this study are selected with empha-
sis on weighability and accuracy of composition. (In cases
where matrix effects or pH are important or where water
solubility is required less desirable compounds may he
used as secondary standards and standardized against so-
lutions prepared from more suitable compounds.)
The tahle lists the final choices for 72 elements and in-
cludes all elements commonly determined by flame spec-
trometric methods. In some instances more than one com-
pound is given. In these cases, the choice is a matter of
availability, matrix or simply convenience. Tabulated
Volume 50. Number 10. October 1973 / 679
 Compounds for Standard Solutions

Element Camoound FormuleWeizht 1. 1WOoom id11 0.1 M l d l l Salvrnf Comments

Aluminum Al mefal Hot, dil. HCI
Antimony KSbOC.H.0e water
.HHm
Arsenic AsrOa dil. HCI
Barium BaCOt dil. HCI
Beryllium Be metal HCI
Bismuth Bi.0l HNOs
Boran HaBOa water
Bromine KRr
~~- water
Cadmium CdO HNOs
Calcium CaCOa dil. HCI
cerium iNH.12CdNO.). water
cevum Cslso, wster
Chmmium KzCrzOi .~~~
wete,
Cobalt Co mste.1 HNOs
copper C" metal dil. HNO,
cuo HCl, hot
Dyspmsium DYsO~ HCl, hot
Elbium E120. HCI, hot
Europium Eva08 HCI, hot
Fluorine NaP - ~ . ~
water
Gadolinium HC1, hot
Gallium HNOs, hot
Geimanium I rn NaOH. hot
Gold Aqua Regia, hot
HF, fusion
HCI. hot
Indium HCI. hot
ISodirn water
Iridium
1mn FImetal HCI, hot
Lanthanum La202 HCI. hot
Lead Ph(NOa1. w&.
Lithium LixCOa HCI
Lutetium LurO. HCI. hot
Magnesium MKO HCI
Manganese MnS0..H20 water
Mercury HgCls water
Molybdenum Moo2 I rn NaOH
N~odymivm Nd103 HCI
Nickel Ni metal HNOs. hot
Niobium HF, fusion
Osmium HISO,. hat
Palladium HNO.. hot
Phosphorus water
Plstinum water
Pofsssium water
wster
water
HCI
HNOI
water
HzSOA,hot
water
Ruthenium water
samarium HCI, hot
Scandium HCl. hot
Sdenium HNOa, hot
Silicon NaOH. Coned.
"P
~~~

Silver water
sodium water
water
strontium HCI
Sulfur water
Tantalum HF. fusion
Tdurium HCI
Terbium HCI, hot
Thallium ..
wste,
Thulium HCI, hot
Ti" Sn metal HCI
SnO HCI
Titanium Ti metal H*SO..
- ~1.1
Tungsten Na,w01.2H.O water
uranium u01 HNO,
HNOs
Vanadium HCl. hot
Ytterbium HCl. hot
yttrium HCI, hot
zinc HCI
zirconium HF. fuaian

0 Ptimsrystandard.
'These compounds conform verywol to the eriterieand approachprimaryatsndard qualify.
c Hizhlv toxie~
~2 ~~ ~~~~

v e r y highly toxic.
.- . -
T h e rare earth oxides. because t h w absorbCox and water vsoorfrom the air. should befreshl~isnited odor to weiehine.
r mp = 29.6.C.The m d s l may be warmed and weighed aathc iquid.
..
I Sodium fluoride solutions will etch gl- andahauld he freshly prepared.
"Sodium Lungstate lore3 both water molecules at llOaC. After drying. F.W. = 293.68,lWO ppm = 1.5962 8, 0.1 m = 29.383 g. The water ianot rapidlyregained hut thecampound should
be kept in adosiccator after drying and should bo wclghedquickly once it iaremoved.
1 Zirconium and hafnium compounds were not investigated infhe laboratory. ThefollowingmcthSods have been recommendedlordissolutian ofrirconium and hafnium (10).
1 . m gof the powdered metal is placed in a platinum dish with 6-10 ml of vator and 1-2 ml of HFi1:51 andcovered v l t h a platinum lid or s parstflned wafehglars. Once di8aolved. the
fluorine may he removed by adding 1-2 ml ofsulfuric acid (cold1 and evaporating t o d e n s ~fumes or todryness ifrewired.
A fusion method may also be used. A5-10fold ex-of K2SzOli-rplaead in a platinum or quartz crucible along Mfh thosample. After moltingtoa homogeneous molten mssr in a muffle
furnace or burner the fusionpmdurf isdi~solvedin 2Nsulfuric acid.
A third method avoids the use of platinum ware The sample of the metal is finely ground and plseed in a smsll heat-resistant beaker. Two to four g a m s of ammonium sulfate and 3-6
ml of sulfuricacid arc then added. A homogeneous melt is obtained on s hot plate and dissolved in 2Nsulfuric acid.

680 / Journal of Chemical Education

with each compound is the formula weight, the weight re-
quired to prepare 1 1 of 10M) ppm solution, the weight re-
quired to prepare 1 1 of 0.1 M solution, suggested solvents
and comments concerning toxicity and solution prepara-
tion. The solvent listed is used to bring the compound
into solution using as small a volume as possible. The so-
lution is then brought to volume with distilled or deion-
ized water. All acids are concentrated unless otherwise
specified and should be analytical grade. Note that for
some compounds dilute acid is specified in preference to
concentrated. Although the solvents in the table have
been shown to he satisfactory, they are by no means in-
clusive and other acids or bases may he utilized in many
cases. For accurate work, compounds should always he
brought to constant weight by drying a t 110°C prior to
weighing.
Recently an excellent compilation has appeared which
(12) Dean, J. A . and Rains, T. C.. (Editors), "Flame Emission and Atomic Absorption
is complementary to this work (12).
Literature Cited
111 Rosin. J.. "Reagent Chsmieak and Standards."Srh 4..D. van Nostrand compa-
ny, In<., Plineeton. 1967.
12) Gabb. M. H., end Latchem. W. E., "A HandbmkofLaboratary SoluBons,"Chem-
ical Puhlishin~Company.NowYork, 1968.
(3) Stocher, P. G.. (Editor), "The Merck Index," 6th pd.. Merek & Co.. Ine.. Rahway,
N ., .""".
"., ,em
(4) Weart, R. C., "Handhwk of Chemistry end Physics." 50th ed.. The Chemical
R u b b r Co., Cleveland. Ohio, 1970.
( 5 ) Sidesick, N. V., "The Chemical Elements and Their Comoounda," Clsrendon
& u , Oxford, 1950.
Buacv, A. I., Tiptsoua. V. G., andinanov, V. M.."Handbookof the Analylieal Chem-
istry of the Rare Elemcnra;' (Tmnalotor Schmorak, J . ) Ann Arbor-Humphrey
Science Publishers, Ine., Ann Arbor, Michigan. 1970.
Viekary, R. C., "Chemistry oftheLanthsnons,"AcademicRass,New York. 1953.
Schoeller, W. R.. and Powell, A. R., "The Analysis of Minerals and Orenof the Rarer
Elements," 3rdod.. Charlea Griffen & Company, London, 1955.
Yost. D. M.. Russell. H.. Garner. C. S.. "The Rare-Earth Elements and Their
Compounds."John WilW & sons, Ine., New York, 1950.
Elinson. S. V., and Potrou. K. I., "Analyticsl Chemistry of Zirconium and Hafnium."
(Tramlotor: Kanor. N.1 Danier Daveyand Company, Inc., New York, 1965.
Gibalo, I. M.. "Analytieel Chemistry of Niobium and Tantalum" (Tramlotor:
Schmnak, J.) Ann Arbor-Humphrey seienec Publishen, A"" Arbar, Michigan,
.....
lW"
Spectrometry. Vol. 2, Marcel Dekker. Ine.. NewYork. 1911.

J MnSO.HsO may bedriedst 1IWC without losing the water ofhydration.

*Niobium and tantalum pentorides ere slowly aolublc in 4Wb HF. The addition ofHlS04 accelerate8 thcaolulon prweaa. They may alao he diesolved by a fusion technique. K&OI is
an often used flux. The pentaridea are fully derompmed at 650-8WC in the presence of a n a l o f o l d amount ofpotaarivm pyrosdfafe. Aquanzor porcelain crucible is auitablc and there-
rulting melt may bedissolved insulfurie acid (II).Thesuthom have usedeold HF/H,SO.sueeessfully in plastic beakamwitha IO-hraolukiontime.
'Antimony potauium tartarate lmesthc %Hz0 with drying sf llOaC. After drying, F.W. = 324.92, IWO ppm = 2.6687~01m = 32.492 g. The water ia notrapidly regained but the com-
poundshould be k w t inn desiccator after dryingand should b wei~hedquickly once it inremoved The dried compound is wafer aoluble.
-When kept dry, silver nitratecryrtals are not affected by light. Solutionsof silver nitrate should hestored in bm*n bottles.
"These compoundsare sold as primary standard8 by the National Bureau ofstandard$. Offiee of Stsndard Reference Materials, Washingtan. D.C. 20234.
OBoric acid may be weighed aecvrstely directly from the bottle. It will 1- 1 H 2 0 moleeule st 1W.C and a second 4 0 mol~eulcat spproximately 13C-14O.C and is difficult todry tos
canatant weight.

Volume 50, Number 10, October 1973 / 681