Silver Chloride Dissolution in AR

WET ANALYSIS OF GOLD-SILVER ALLOYS OF
HIGH GOLD CONTENT1

EARLE R. CALEY AND LOWELL W. SHANK
Department of Chemistry, The Ohio State University, Columbus, Ohio
ABSTRACT
Gold-silver alloys dissolve completely in mixtures of hydrochloric and nitric acids
acids containing potassium chloride in high concentration. In an analytical procedure
based on this observation, silver is separated and determined as the chloride, and gold
as the metal after reduction with sulfite. Analyses of test alloys, synthetic mixtures, and
ancient objects showed that this new procedure is practicable and that results of satis-
factory accuracy can be obtained.
INTRODUCTION
Because neither hydrochloric acid nor nitric acid attacks gold-silver alloys of
high gold content, and because mixtures of the two acids do not dissolve all such
alloys completely or rapidly, the assay method used for centuries has been first
to fuse samples of these alloys with sufficient pure silver to bring the gold content
down to about 25 percent, and then to treat this with nitric acid to separate the
gold from the silver and base metals. This standard method requires special
apparatus for the fusion step that may not be available in laboratories in which
gold alloys are infrequently analyzed. In an alternate method here described,
the fusion step is eliminated.
A hot mixture of hydrochloric acid and nitric acid attacks an alloy of high
gold content, but the silver chloride that is formed coats the unattacked alloy
so that decomposition is incomplete unless the proportion of silver is unusually
low or unless the treatment is continued for a long time with successive fresh
portions of the acid mixture. However, if potassium chloride is present in suf-
ficient concentration in the acid mixture, no separation of silver chloride occurs
and the alloy dissolves completely in a conveniently short time.
SOLUBILITY EXPERIMENTS
The solubility of silver chloride in aqueous solutions is increased by high
temperature, high chloride concentration, high hydrogen-ion concentration, and
by combinations of these conditions. This increase is largely due to the forma-
tion of soluble complex ions such as AgCl^, so the maximum effect occurs when the
active concentration of chloride ions is as high as possible. Results from experi-
ments on the simultaneous effect of high temperature and high alkali-chloride
concentration are shown in table 1. In these experiments a boiling salt solution
containing an excess of solid silver chloride was refluxed until no more dissolved.
An aliquot of clear solution was withdrawn with a heated pipet and allowed to
cool to room temperature, which caused much of the silver chloride to precipitate.
The mixture was then diluted with sufficient water to precipitate the remainder
quantitatively. After coagulation by stirring and standing, the silver chloride
was filtered off, washed, dried, and weighed in the usual way. It will be seen that
the solubility in molar solutions of the different salts is about the same, that it
increases greatly with increase in concentration, and that the degree of increase
is markedly different for the individual salts, probably because of the differences
in their ionic character in concentrated solutions. Potassium chloride is clearly
the most effective for dissolving silver chloride. Although ammonium chloride
is somewhat less effective, its use might be considered more desirable in analytical
procedures because of the ease with which it can be removed. However, it is not
Manuscript received September 7, 1967.
THE OHIO JOURNAL OF SCIENCE 68(2): 100, March, 1968.
No. 2 ANALYSIS OF GOLD-SILVER ALLOYS 101
effective for preventing the separation of silver chloride from hot mixtures of
hydrochloric and nitric acids because of the rapidity with which the ammonium
ion is oxidized.
Results from similar experiments on the solubility of silver chloride in boiling
hydrochloric acid and in boiling hydrochloric acid containing potassium chloride
TABLE 1
Solubility of silver chloride in solution of alkali chlorides
at the boiling point
Mg of AgCl dissolved in 50 ml of solutions

Salt of stated molarity
1.0 M 3.0 M 5.0 M
KCl 11 123 614

NH4C1 12 111 472
NaCl 10 82 292
LiCl 9 38 100
are shown in table 2. It will be seen that its solubility in the molar acid is about the
same as in molar solutions of alkali chlorides, and that its solubility increases
regularly with increase in concentration. However, as is apparent from a com-
parison of the data in tables 1 and 2, the solubility of silver chloride in 3.0 and 5.0
molar solutions of the acid is less than in 3.0 and 5.0 molar solutions of any salt
except lithium chloride. The solubility of silver chloride in hot hydrochloric acid
solutions containing potassium chloride is greater than in hot potassium chloride
TABLE 2
Solubility of silver chloride at the boiling point in
hydrochloric acid and in hydrochloric acid 3.0 M
in potassium chloride
Concentration Solubility in Solubility in

of acid M acid alone acid plus KCl
nig/50 ml mg/50 ml
1.0 11 222
2.0 33 433
3.0 66 698
4.0 112 —
5.0 175
solutions of the same concentration. This effect is limited by the decrease in the
solubility of potassium chloride as the concentration of the acid increases. As
is indicated in table 2, it is no longer possible to maintain the concentration of the
salt at 3.0 molar in acid solutions more concentrated than about 3.0 molar. In
spite of this limitation, the solubility of silver chloride in hot acid of higher con-
centration nearly saturated with potassium chloride is such that a sample of gold-
silver alloy containing 50 percent silver and weighing as much as 0.5 gram will be
completely dissolved by a conveniently small volume of this solvent.
ANALYTICAL PROCEDURE
Take a sample of fine chips or drillings that weighs no more than 0.5 gram,
place it in a 250-ml Erlenmeyer flask, add 10 grams of potassium chloride, 40 ml
102 EARLE R. CALEY AND LOWELL W. SHANK Vol. 68
of concentrated hydrochloric acid, and 10 ml of concentrated nitric acid. Heat

just below boiling until the sample dissolves completely. If potassium chloride
crystallizes out before the sample dissolves, add just enough water to redissolve
the salt. Add 10 ml of concentrated nitric acid and evaporate to a thick slurry.
Add 5 ml of concentrated hydrochloric acid, again evaporate to a thick slurry,
and repeat this addition and evaporation. Add 25 ml of cold water slowly with
agitation to precipitate and coagulate most of the silver chloride. Add 125 ml
more water to complete the precipitation and set aside with occasional stirring
until all the silver chloride coagulates. Collect the precipitate in a weighed filter
crucible, and filtrate and washings in a 400-ml beaker. Wash with cold 0.01 M
nitric acid, dry to constant weight at 150° C, and weigh.
Evaporate the filtrate and washings to a volume of about 75 ml, cool to about
50° C, and add 5 ml of concentrated hydrochloric acid, followed by 25 ml of satu-
rated sodium sulfite solution. Boil and stir the mixture for about two minutes
and allow it to stand below the boiling point for about 45 minutes. If any pink
color is still visible in the solution, heat to boiling, add 1 ml of concentrated hydro-
chloric acid followed by 5 ml of saturated sodium sulfite solution, and allow to
stand below the boiling point for 15 more minutes. After cooling, collect the gold
in a weighed filter crucible, wash with hot 0.1 M hydrochloric acid, dry briefly
at 120° C, ignite to constant weight at full red heat, and weigh.
Notes on Precedure
The purpose of the repeated evaporations and additions of acids after the
sample dissolves is to remove most of the hydrochloric acid, and all of the nitrosyl
chloride and oxides of nitrogen. If the silver chloride is not completely coagulated,
some may appear in the nitrate when this is evaporated, and another filtration
may be needed to recover this additional precipitate. The filtrate from the separa-
tion of the gold may be used for the determination of copper and other base metals
by various procedures. If copper is to be determined electrolytically, all the
chloride must be removed. This may be done by adding 10 ml of concentrated
sulfuric acid and evaporating until dense fumes of sulfur trioxide evolve for a
few minutes.
TEST ANALYSES
Results of analyses of two gold-silver alloys are shown in table 3. These
alloys were made in the Department of Metallurgy, The Ohio State University,
TABLE 3
Test analyses of alloys
Alloy Sample Solution Gold Silver

No. Weight Time Pound Found
Gram Min. % %
1 0.1293 120 49.88 50.00

1 0.1094 55 50.00 50.08
2 0.2495 55 63.37 36.11
2 0.2010 55 63.38 36.13
for an earlier investigation, by melting together weighed amounts of the pure

metals in an induction furnace. Because of the possibility of differential loss of
metal by volatilization, these alloys could not be taken as reliable standards for
testing the accuracy of the procedure. Instead, they were used primarily to test
its practicality, especially with respect to the time needed to dissolve samples.
No. 2 ANALYSIS OF GOLD-SILVER ALLOYS 103
It will be seen that the first sample, which was in the form of a few coarse pieces,
took two hours to dissolve, whereas the others, in the form of small chips, took
less than an hour. Samples in the form of fine drillings or filings require still less
time.
These test analyses also indicate that the procedure is capable of yielding
precise results. In spite of the uncertainty about the exact composition of these
alloys, the results obtained on No. 1 agree well with its stated gold content of
50 percent. The results for the other are over 1 percent off from its stated gold
content, and the summation is low, apparently in part because of the presence of
nonmetallic inclusions.
As a more reliable test of the accuracy of the procedure, test analyses were
made of synthetic samples prepared by mixing weighed amounts of pure granular
gold and silver obtained by the elctrolytic reduction of solutions of gold chloride
and silver nitrate. The results are shown in table 4. It will be seen that the
TABLE 4
Test analyses of synthetic samples
Sample Sample Gold Gold Silver Silver

No. Weight Taken Found Taken Found
Gram Gram Gram Gram Gram
1 0.3998 0.3243 0.3247 0.0755 0.0754

2 0.4004 0.3194 0.3189 0.0810 0.0811
3 0.4588 0.3409 0.3403 0.1179 0.1181
4 0.4602 0.3433 0.3425 0.1169 0.1169
absolute errors for silver are small, the average being only 0.0001 gram when the
direction of the individual errors is neglected. The absolute errors for gold are
larger, the average being 0.0006 gram when the direction of the errors is neglected.
However, the relative errors on this same basis are not very different, the average
being 1.1 parts per thousand for the silver and 1.8 parts per thousand for the
gold. The generally negative error for the proportion of gold, as determined by
this procedure, appears to be caused in part by the difficulty of reducing the gold
completely and in part by the manipulative difficulty of collecting all the par-
ticles of finely divided gold.
Results of analyses of two gold objects, in the form of damaged ornaments
from excavations in Mexico, are shown in table 5. The copper was determined
electrolytically in the filtrate from the gold separation. It will be seen that the
results on the two samples of the first object agree well and that the summations
TABLE 5
Analyses of ancient objects
Object Sample Gold Silver Copper Total

No. Weight Found Found Found Found
Gram
1 0.2883 71.59 27.74 0.59 99.92

1 0.1484 71.52 27.81 0.61 99.93
2 0.2671 61.91 37.19 0.94 100.04
104 EARLE R. CALEY AND LOWELL W. SHANK Vol. 68
of all three analyses are very satisfactory. The data indicate that the objects
were made from native gold.
In general, these test analyses show that this new procedure yields satisfactory
results for the determination of the main components of alloys of gold and silver,
or gold, silver, and copper. It has the advantage of requiring no special appa-
ratus or chemicals. Hence it should be very suitable for the analysis of gold
artifacts in museum or field laboratories. In fact the procedure was devised for
this purpose.

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WET ANALYSIS OF GOLD-SILVER ALLOYS OF

HIGH GOLD CONTENT1

Mg of AgCl dissolved in 50 ml of solutions

1.0 M 3.0 M 5.0 M

KCl 11 123 614

Concentration Solubility in Solubility in

of concentrated hydrochloric acid, and 10 ml of concentrated nitric acid. Heat

Alloy Sample Solution Gold Silver

1 0.1293 120 49.88 50.00

for an earlier investigation, by melting together weighed amounts of the pure

Sample Sample Gold Gold Silver Silver

1 0.3998 0.3243 0.3247 0.0755 0.0754

Object Sample Gold Silver Copper Total

1 0.2883 71.59 27.74 0.59 99.92

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