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THE PRECIPITATION OF SILVER CHLORIDE FROM

AQUEOUS SOLUTIONS
PART 2.-KINETICS

OF GROWTH OF SEED CRYSTALS

BY C. W. DAVIES
AND A. L. JONES
Edward Davies Chemical Laboratories, University College of Wales, Aberystwyth
Received 3rd December, 1954
Within a restricted range of concentration, supersaturated solutions of silver chloride
can be prepared in which nucleation does not occur. The growth of silver chloride seed
crystals in such solutions at 25" C has been studied conductimetricallyat various [Ag+]/[Cl-]
ratios. There is no induction period, and the rate of growth is proportional to the total
crystal surface and follows a second-order equation.
The solubility of silver chloride in water at 25"C is found to be 1.334 x 10-5 molejl.,
and the solubility product (zero ionic strength) is 1.765 x 10-10.

It was reported in part 1 1 that supersaturated solutions of silver chloride can

be prepared in which precipitation, if it can occur at all, is imperceptibly slow.
If aged seed crystals are added to these supersaturated solutions no further nucleation occurs, and the growth of the crystals can therefore be observed under ideally
simple conditions. Such experiments are described in the present paper, and lead
to a simple equation for the rate of growth of silver chloride crystals from aqueous
solutions of varying ionic ratio.
EXPERIMENTAL
Crystallization was followed by conductivity measurements, and the apparatus and
materials were as described in part 1. Table 1 gives particulars of the seed suspensions
used.
TABLE
1
suspension
concn. (g AgCI/l. suspension)
mean crystal size Q

C
0.96
4.7

D
0.97

3.5

E
1.20
2.8

Crystal size is expressed as the average length of side of a crystaI, and was examined by
taking microscopic measurements of a hundred particles chosen at random.
In making a run, a known weight of conductivity water was collected in the cell and
brought to temperature equilibrium with the stirrer in operation and a steady stream of
purified nitrogen passing through the cap of the cell. 10 ml of dilute AgN03 solution
were then added from calibrated pipette, and this was followed by a slow dropwise
addition of a similar quantity of KCI solution. The concentrations of these solutions
were adjusted so that (i) the resulting [Ag+]/[CI-] ratio was 1, 2, 4, 0.5 or 0.25, to within
1 % or better, and (ii) that the resulting concentration product was within the limits
determined in part 1 for stable supersaturated solutions. The resulting solution was
allowed to reach temperature and carbon dioxide equilibrium, a process which normally
required about 3 h. Independent experiments showed that thereafter the conductivity
remained quite constant for at least 12 h. When the solution had been at equilibrium
for at least 1 h, a known amount of seed suspension (2 or 5 ml) was added from a quick
delivery pipette, a stop clock was started, and resistance readings were taken, at first at
30-sec and later at less frequent intervals.
Before the seed suspension was added it was swept free from carbon dioxide by shaking
under a stream of pure nitrogen for half an hour. This precaution was essential, as
812

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C. W. DAVIES AND A . L. JONES

81 3

otherwise a slow loss of carbon dioxide occurred in the cell over the period of the
run,producing a change of conductivity comparable in magnitude with that due to the
crystallization.
Experiment showed, howThe stirring rate was usually maintained at 260 rev/&.
ever, that variations within the range 100-500 revlmin were without effect on the results,
and it was also possible to substitute a rapid stream of nitrogen for the mechanical stirring
without altering the rate of crystallization. The agitation was evidently sufficient to
keep the solution mixed and the h e crystals in uniform suspension, but had no inffuence
on the mechanism of crystal growth.

RESULTS
EXPERIMENTS
AT EQUAL IONIC coNcEwRAnoNs.-Seven runs were carried out, four
with 5 ml and three with 2 ml of suspension C added. The available concentration range
was between the solubility product, 1.8 x 10-10, and the critical supersaturation for spontaneous nucleation, 3.1 x 10-10, and in these runs the initial concentration product was
varied between 2.2 and 2.8 x 10-10. Two experiments are shown in fig. 1, every fifth
reading only being plotted on curve 2. Crystallization begins as soon as seed is added,
there being no induction period. For these two experiments the initial concentrations
were nearly the same, but 5 ml of seed suspension were used in curve 1 and only 2 mi
in curve 2. The initial rate of crystallization is proportional to the quantity of seed present,
and the same is true of the other runs.

Minutcr

FIG. 1.-Typical

crystallization runs ; seed added at time t = 0.

In fig. 2 the square root of the initial rate of crystallization per ml of seed suspension
is plotted against the initial concentration. A good straight line is obtained which extrapolates to the value of 1 - 3 7 x 10-5 mole/l. for zero rate. This is, within the experimental
error, the value found in part 1 for the solubility of silver chloride, so the initial crystallization rates obey the equation :
- dC/dt = ks(C - C O ) ~ ,
(1)
where s is the amount of seed added, C is the ionic concentration and COthe solubility.
To see if this second-order equation is obeyed throughout the crystallization, tangents
were drawn to the curves at intervals, and the corresponding concentrations were calculated from the conductivities. The points obtained in this way are also plotted in fig. 2,
and allowing for the somewhat higher error involved in the calculations they also lie
on the same line. Over 75 % of the total possible precipitation was followed in the

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814

P R E C I P I T A T I O N OF SILVER C H L O R I D E

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longest of these runs, so the whole crystallization probably takes place in accordance with
eqn. (1). The constant s in this equation can be regarded as representing the area available
for the deposition, for the amount of AgCl deposited in any run never exceeded 1 x 10-6
mole, and amounted to only 1-3 % of the total amount of seed present.
The experiments with only 2 ml seed suspension were too slow to follow much beyond
half-completion, and for these runs eqn. (1) was tested by calculating the conductivity
value corresponding to 50 % precipitation, and reading the time of half-completion from

c
FIG. 2.-Initial
101,

10'

m o l e / I.

rates of crystallization, 0 ; subsequent points for expt. 27, A ; 99,

; 102,O. (Rates in mole x 108 1.-1 min-1 ml-1 seed suspension).

v;

the curve. For a second-order equation these times should be inversely proportional
to the initial supersaturation, and this was found to be true. The values obtained were
expt.
C-CO (mole/l. x 106)
t+ (min)
(C--Co)t*

96
3-22
52.0
168

98
2-69
63.0
169

100
2-07
82.5
171

THESOLUBILITY OF SILVER CHLORIDE AT 25" C.-The value given in part 1 needs slight
revision in view of the above results. Application of eqn. (1) to the data given in table 1
of part 1 shows that for expt. 45 and 76 as much as 7 % of the precipitable AgCl remained
undeposited when the experiments were stopped. Smaller corrections are required for
the other three points, and the effect of these is to reduce the mean value of S (the concentration solubility product) from 1.82 to 1-78 x 10-10 (mole/l.)2. Neglecting one
discordant point in table 2, the mean value of S from this second series is 1.796 x 10-10.
The extrapolated solubility from fig. 2 of the present paper gives S = 1-787 x 10-10,
in agreement with the mean. This is the concentration product in the presence of potassium
nitrate of concentration (1.60 f 0.1 1) x 10-5, and if the ionic strength Z=(294&0.1) x 10-5
is inserted in the Debye-Hiickel limiting equation, the value 1,765 x 10-10 is obtained
for the solubility product of silver chloride at zero ionic strength. In the same way,
1-334 x 10-5 mole/l. is derived for the solubility of silver chloride in water at 25". These
values are in remarkably good agreement with those given recently by, respectively,
Guggenheim and Prue,2 and Gledhill and Malan.3
AT NON-EQUIVALENT CONCENTRATIONS.-Additional
runs were carried
EXPERIMENTS
out at initial [Ag+]/[Cl-] ratios of 2, 4, 0.5 and 0.25. Suspension D was used in these
experiments. Eqn. (1) cannot apply where the ionic concentrations are unequal; but
we may rewrite it in the form
- dC/di =z kshz,
(2)
where A represents the number of moles per litre to be deposited before equilibrium is
reached, and necessarily has the same value for the silver and chloride ions whatever their

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C . W. D A V I E S A N D A , L . J O N E S

815

actual concentrations. A test of this equation is shown in fig. 3, where four runs at
different ionic ratios are compared ; A, calculated from the relationship
(Cl - A)(C2 - A) = S = 1.787 x 10-10,
is plotted against the square root of the velocity. Within the errors of calculation the
points again lie on a straight line, which passes through the origin.
The slopes shown in fig. 2 and 3 are not the same, but this does not reflect a variation
in k ; it is due to the use of different seed suspensions in the two series of experiments.
Equal weights of AgCl seed were added in all cases, but suspension D consisted of smaller
seed. The total surface it represented should therefore be greater than that of suspension
C by the approximate factor 4-7/35 the ratio of the linear particle dimensions (assuming
uniform cubes) ; the slopes of fig. 2 and 3 are in reasonably good agreement with this,

lo5

molc/l.

FIG. 3.
0 expt. 104, [Ag]/[Cl]= 0-5 ;
4 Expt. 103, [Ag]/[CI] = 2 ;
D expt. 106, [Ag]/[Cl] = 0.25 ;
0 expt. 105, [Ag]/[Cl]= 4 ;
(rates in mole x 108 1.-1 min-1 ml-1 seed suspension).

as are also further unreported measurements using suspension E. Within the possible
error, therefore, k has the same value in eqn. (1) and (2). The actual surface area can
be roughly calculated, using the data of table 1 and the value 5.6 for the density of silver
chloride : 4 thus for suspension C the approximate value 2.2 cm2 ml-1 suspension is obtained. Giving s this value in eqn. (2), the velocity constant k has the approximate value
15 per cm2 with A in moles per litre and time in sec.
AGEING
OF SEED CRYSTALSAT NON-EQUIVALENT CONCENTRATIONS.-A
number of further
runs were made in which the seed, before use, was equilibrated with saturated solutions
in which the ionic ratio was varied up to a value of 10/1. After this treatment the seed
behaved precisely as before, and the runs fitted eqn. (2) without modification.

DISCUSSION
At its simplest, the crystallization of a sparingly soluble salt from solution
would seem to involve the following three mechanisms : (i) the diffusion of solute
to the surface, (ii) the deposition of ions on the crystal face, (iii) the opposing
process of solution.
According to eqn. (2) the rate throughout the crystallization process is governed
by the concentration that each ion will eventually reach at equilibrium : A represents the difference between this value and the momentary ion concentration.

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816

P R E C I P I T A T I O N OF SILVER CHLORIDE

This at first suggested that the rate-determining process in our experiments was
one of diffusion : processes (ii) and (iii) were sufficientlyrapid tomaintainaneffective
concentration corresponding to saturation of each ion at the surface, and the rate
of growth was governed by a concentration gradient A16 through a diffusion layer
of thickness 8. This diffusion hypothesis, however, would lead to a first-order
equation, and is therefore unacceptable ; for silver chloride ion-pairs wodd diffuse
to the surface under a common concentration gradient, and their rate of arrival
would be given by the classical Nernst equation, w = DsA/S, where D is the diffusion coefficient of silver chloride. Much evidence that the solution in contact
with a growing crystal is supersaturated5 also tells against diffusion being the
governing factor in most crystallization processes, and the independence of the
rate on conditions of stirring points in the same direction.
Since mechanism (i) is not rate-determining, we turn to (ii) and (iii). The
saturation of a solution is frequently cited as an exampIe of kinetic equilibrium,
leading to the following formulation (for equal concentrations of silver and
chloride ions) :
rate of crystallization of AgCl = kls C2,
= k2s.
rate of solution of AgCl
In a saturated solution these rates are equal, and so k2 = kl C$. In a supersaturated solution, assuming that diffusion exerts no influence, the net rate of
deposition will thus be given by
- dC/dt = Icls(C2 - Co2).
This is contrary to our findings. In any case this analysis into two independent
opposing processes does not give a correct picture of conditions in a heterogeneous
system, where we are not considering the statistical result of a number of isolated
chemical actions, but the net change at a fixed reaction site.
Special conditions prevail at the interface where the reaction is occurring, and
we may therefore postulate an adsorption layer, and formulate the kinetics in
terms of a stationary concentration of silver and chloride ions in the adsorbed
phase. We find that this will lead to the observed results on the following two
assumptions :
(1) A crystal in contact with an aqueous solution always tends to be covered
with a monolayer of hydrated ions. Secondary adsorption on this monolayer is
negligible. Crystallization, i.e. incorporation of further units into the crystal
lattice, can only occur if the resulting configuration satisfies this condition.
(2) Crystallization of silver chloride occurs through the simultaneous dehydration of pairs of silver and chloride ions.
In terms of this picture, an unsaturated solution is one in which hydrated ions
leave the surface faster than they are replaced from the solution, causing further
hydration at the surface. When the surface reaches equilibrium the rate of
adsorption of ions from the solution becomes just sufficient to maintain the
monolayer of hydrated ions intact, and it must be assumed (to avoid squared terms
in the rate equation) that every ion striking the surface from a saturated solution
enters this mobile adsorbed monolayer. For a saturated solution we can therefore write: rate of adsorption of Ag ions = kls[Ago+], and similarly for the
chloride ions. From a supersaturated solution the ions reaching unit surface
do not all enter the adsorbed monolayer, and the remainder, kl([Ag+J - [Ago+]),
are available for deposition; i.e. they either suffer elastic collisions at the surface
of the monolayer or, in the event of the simultaneous arrival of a silver ion and a
chloride ion at a site of growth the underlying ion pair can become dehydrated,
and we obtain
dC/dt k3([Ag+]- Co)([Cl-] - CO),
which is eqn. (1).

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C . W. DAVIES AND A . L. JONES

817

In the foregoing we have assumed that the adsorbed monolayer contains

equal numbers of silver and chloride ions, so that there is no difference of electrical
potential between crystal and solution. This will not generally be true. Even if
the concentrations of silver and chloride ions in a saturated solution are equal
there will be a difference between the numbers of silver and chloride ions adsorbed
owing to the difference in the adsorption energies of the ions. This difference
will be too small to affect the validity of the equation just developed. It is important, however, to consider cases in which the concentrations of silver and chloride
ions in the solution are unequal. Suppose a seed crystal is immersed in a solution
in which [Ag+]/[Cl-] = r, where r > 1. At first more silver than chloride ions
will be adsorbed, and a potential difference # will be established between adsorbed
layer and solution. The equilibrium value of # will be such that silver and chloride
ions enter the adsorbed layer in equal numbers. An electrical double layer now
surrounds the crystal, and the former equations must be replaced by
availability of Ag ions at the surface = kls[Ag+]exp (- $(RT)
availability of Cl ions at the surface = kls[Cl-] exp (#/RT).
Since these are equal, exp ($/RT)= [Ag+l*/[Cl-]*= t-4.
The number of ions of each type entering the monolayer in unit time is as before
CO,and the rate of crystallization becomes
- dC/dt = ks([Ag+Jr-*- Co)([cl-]~*- CO)= kls([Agf]*[Cl-]* - C O ) ~ .(3)
If ro is the final ionic ratio after equilibrium has been reached, the equilibrium
concentrations of silver and chloride ions are respectively Coro* and Cora-* for
[Ag+][CI-] = C02 and [Ag+]/[Cl-] = ro. Eqn. (2) can therefore be written
- dC/dt = ks([Ag+] - Coroi)([Cl-] - Cora-*),
and it differs from the equation just derived in containing the equilibrium ionic
ratio instead of the actual ionic ratio.
A comparison of the two equations shows that they are not compatible; if
k in eqn. (2) is constant, kl of eqn. (3) will vary by up to about 3 % during the
course of a run, and vice versa. This is within our experimental error, however,
and experimentally it is impossible to prefer one equation to the other; fig. 3
shows the good agreement with eqn. (2), and eqn. (3) is illustrated in part 3
(following paper). When runs at differing ionic ratios are compared, k (eqn. (2))
remainsconstant; kl, on theother hand, depends on the ionic ratio, and has its
maximum value when this is unity. Eqn. (2) is therefore the simplest representation of the facts within the restricted range of concentration and ionic ratio that
we were able to investigate; but from the mechanism of crystallization outlined
above a variation in kl will be expected, and will reflect the restriction, through
adsorption, of the number of sites available for growth. Further data in conformity
with this idea are given in part 3.
We thank the D.S.I.R. for a grant to A. L. J. (1946-49) during the tenure of
which this work was carried out.
1 Davies

and Jones, Faruduy SOC.Discussions, 1949, 5, 103.

Guggenheim and Prue, Trans. Furuday SOC.,1954, 50,236.
Gledhill and Malan, Trans. Fizroduy Soc., 1952,48,258.
4 Landolt-Bornstein, Tabellen, 5te. Aufl., I, 307.
5 Miers, Proc. Roy. SOC.A , 1930, 71, 439; see Bunn, Faruday SOC. Disczrssions,
1949, 5, 132. Wells, Ann. Reports, 1946, 43, 73.

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