SODIUM DITHIONITE, DECOMPOSITION IN AQUEOUS SOLUTION

AND IN THE SOLID STATE1

ABSTRACT
T h e decomposition of sodium dithionite has bee11 investigated in allialine aqueous solutior~.
Under these conditions it decomposes by a first order reaction with a rate constant of 4.5X
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min-I a t 88.5" C and a n activation energy of 26.5 kcal/g-molecule. T h e ionic strength,

and the concentration of the sodium hydroxide also present, affect the rate t o some extent. A
possible mechanism is suggested. T h e decomposition of solid sodium dithionite was also
examined, and was f o u ~ l dt o give the best fit to the equations d e d ~ ~ c assuming
ed random nuclea-
tion, follolved by linear growth of nuclei, with possible ingestion and interference of reacting
zones. The activation energy of nucleus growth is 32 to 33 lical/g-molecule, and that for
nucleation probably between 40 and 45 lical/g-molecule.

T h e deconlposition of aqueous solutions of sodium dithionite was examined by I<.

and E . Jellinek (1). T h e y established that the products were sodium thiosulphate a n d
bisulphite, so t h a t the equation for the reaction is:
2Na2S20r + H?O --t + 2NaI-IS03.
N.12S~03

T h e quantities ol the various products agreed with this equation. They illeasured the
rate of decon~positionin solutions containing varying, b u t usually large, amounts of
For personal use only.

sodium bisulphite. Froin the ionization constants of sulpl~urousacid (2), the p H of these
solutions inust have been about 4.5. T h e y found a second order reaction, fairly rapid
eve11 a t room teniperature: the rate constant was 0.044 (g-m~lecule/l.)-~ min-I a t 32' C.
T h e rate constailts a t various temperatures give oilly a nloclerately straight line in a
plot of log (rate constant) against l/temperature (they did not themselves p u t their
results in this form); the activation energy appears to be close to 8 kcal/g-molecule.
This is a remarkably low activation energy, when it is reniembered t h a t the inechanisnl
proposecl is one involving the collision of two d o u b l ~ .charged ions, follo\ved by the
breaking of a t least one chemicr~lboncl. T h e details of the reaction are not elltirely clear,
but whatever mecl~anismis suggested niust include a t least one bond rupture. T h e n ~ o s t
obvious solution of this clifficulty woulcl be to supposc t h a t a t the p H used, the dithionite
is partly present a s HS201-, or even a s H2S2OZ1 molecules, and t h a t these react. Accord-
ingly, experiments nvere imacle on the decomposition of sodium dithionite in alkaline
solution; and, as will be seen below, these show t h a t the rates in all<aline solution are
quite clifferent fi-om those reported by I<. and E. Jellii~ek.T h e reaction was examined
over a range of ionic strength and temperature.
T h e decomposition of solid sodium dithionite has been examined by Deines and
Elstner (3), who found the products to be sodiuin thiosulphate and sulphite and sulphur
dioxide. This is sufficiently siinilar t o the reaction in solution t h a t it seemed worth while
to obtain seine quantitative information on the decon~positionof the solid, pal-titularly
in order to coinpare the activation energies of the reactioil under the different circum-
stances.
E S P E R I MENTAL
T h e chief difficulty in these experiillents is t h a t sodiunl dithionite solutions can be
'Manzlscript ~.eceized April 17, 1959.
Contribution from the Depurtmct~tof Clze71tistry, Uniuc~sityof Toronto, Toronto, O~ttario,Cu7zczda.
Can. J. Chem. Vol. 37 (1959)

1567
 1568 CANADIAN JOURNAL O F CHEMISTRY. VOL. 37, 1959

oxidized by at~nosphericoxygen, so air must be rigorously excluded, both during the

run, ancl during nlanipulation of samples. T h e apparatus used was similar to t h a t of
K. and E. Jellinelt, modified only in details. T h e solutions were made up in a tlaslt under
a positive pressure of purified nitrogen. During the run this flask was immersed in a
water thermostat, and the contents were stirred with a mercury sealed stirrer. A t inter-
vals samples were sucltecl u p into a nitrogen-filled burette, and then a measured volume
of solution was iininediately run into excess oxidizing agent. T h e details of the analysis
are given below.
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In t h e experiments with solid sodiunl dithionite, t h e apparatus consisted of a long

pyrex tube, with a sintered glass dislt fixed across the middle of it. T h e tube was wound
with suitable resistance wire and insulation, and a therinocouple was placed just above
the glass dislt. During the actual run the thern~ocouplewas embedded in the sodium
dithionite. T h e temperature a t the thern~ocouplewas maintained constant by connecting
i t t o a potentiometer, and sending the off-balance current through a light-and-mirror
galvanonieter, t h e light being reflected on t o a photocell. T h e photocell activated a relay
which introduced a small extra resistance into the heating circuit when the temperature
rose. T h e temperature was thus controlled to 0.1' C. Nitrogen was passed through the
tube and disk, a n d , for a run, sodium dithionite was placed on the disk. As soon as i t had
come to temperature, a sample was removed by a small glass scoop, weighed, and analyzed ;
further samples were talten a t suitable intervals.
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In t h e solution runs, the solutions were always ltept alkaline with sodium hydroxide.
T h i s is slowly used up, a s the total reaction is:

b u t the runs were never carried beyond the point where the sodium hydroxide was
exhausted. Tlle ionic strength n7as adjusted by addition of sodium fluoride. T h i s salt
was chosen because it did not interfere with the analyses, and is of a simple ionic type.
As the equation sl~ows,the ionic strength rises during the reaction. I n the results given
below, the initial ionic strength is recorded. i\/Iost of t h e runs were ltept fairly short, so
t h a t the change in ionic strength was not above 0.05, a s i t was expected t h a t the rate
~vouldvary considerably with ionic strength. As it turned out, there is some such varia-
tion, b u t it was not very large. For the most part, evidence of the order of the reaction
was obtained by starting runs a t different dithionite concentrations, b ~ in~the t run shown
in Fig. 1, the analyses were contiilued long enough t o give fairly definite evidence of this
froin this run alone.

Time (rnin)
FIG.I.
 LISTER AND GARVIE: SODIUM DITHIONITE 1569

The analysis for dithionite in alltaline solution presents sonze difficulties that are not
encountered in neutral or wealdy acid solution. K. and E. Jellinek used the reduction of
ammoniacal copper (11) sulphate for their analyses. In alltaline solution this reagent
gives a heavy black precipitate (probably a sulphide) with dithionite, and the method is
impracticable. Hahn (4, 5) used titration with ferric chloride, in the presence of a inixed
iildicator of potassium thiocyanate and ferricyanide, but this was found to give irregular
results in alltaline solution. However, it worked well for the analyses of solid sodiunz dithio-
nite, and was used in runs with the solid. The method fi~lallyused in the solution runs
was that due to Smith (6). A known volume of dithionite was run into excess a~nmoniacal
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silver nitrate; silver is then precipitated. This was filtered off,washed, dissolved in nitric
acid, and titrated with chloride by the Volhard method. T h e chief difficulty was that
sometimes the precipitate was so finely divided that filtration was virtually impossible,
and samples were occasionally lost because of this.
The reagents used were all of analytical reagent quality, with the exception of the
sodium dithionite. T h e purest available solid was about 90% sodium dithionite, the main
impurities being the deconzposition products, sodium thiosulphate and sulphite. Ke-
crystallization did not much improve this as some deconzposition always occurred.
Solutions were made from this, and were then analyzed in order to be able to calculate
the ionic strength. This was then adjusted to the desired value by adding sodium fluoride.
For personal use only.

RESULTS
The runs were generally not long enough to distinguish u~lambiguouslythe order of the
reaction solely from one run. Accordingly in Table I the results are given in the forin of
the best values of the first order rate constants (kl), and the second order rate constants
(kz),obtained in the usual way from a plot of time against log (concentration) or (con-
centration)-'. This table also gives runs a t various ionic strengths, a t various temperatures,
and a t various initial sodiu~nhydroxide concentrations.

TABLE I
Decomposition of s o c l i ~ ~dithionite
m in aqueous solution
- .
-

Initial Initial ku,

Temp., Initial (K\;x?S?04), ( NaOH), k~, (g-molecu le/l.)-'
Run "C ionic strength molar molar min-' min-I

T h e first thing that is apparent froin this table is that the reaction is first order in
dithionite. Runs 1 to 4, or 5 to 7, where all other variables are kept constant show this
clearly. Figure 1 shows a plot of log (concentration) and (concentration)-I against time
for run 16. This gives a better straight line for a first order reaction. This, as well as the
great differences in over-all rate, proves that the reaction in alkaline solution is not the
 1570 CANADIAN JOURNAL O F CHEMISTRY. VOL. 37. 1959

same as that examined by K. and E. Jellinek. The obvious explanation of this is that
under the conditions of their experiments the solution contained HSBOQ-or H2S201,and
that these decompose faster than S204--. Similar behavior is, of course, found with other
acids and their salts, e.g. thiosulphates and hypochlorites. There seein to be no reliable
values of the ionization constants of dithionous acid, so it is iinpossible to calculate the
concentrations of HS2Oc or H2S204 in I<. and E . Jellinek's experiments. With an activa-
tion energy as low as 8 ltcal, as calculated from their results, it seems quite probable
that molecules of dithionous acid are reacting.
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The effect of varying coilcentrations of sodium hydroxide can be seen froin runs 8, I ,
9, and 5. T h e rate increases somewhat a t higher sodium hydroxide concentrations, but
the change is very small a t lo~verconcentrations. Presumably hydroxide ions catalyze
the reaction to seine extent, but the effect is not proportional to their concentration.
Ionic strength was varied in runs 10 to 12, taken together with earlier runs a t an ionic
strength of 0.7. The results show a moderate change in rate with ionic strength, higher
ionic strengths giving increased rates. Soillewhat similar behavior is, of course, found in
other ionic reactions.
Variation in temperature in runs 13 to 15 gave rate constants which show a reasonably
linear plot of log k against 1 / T of the usual sort. T h e activation energy is 26 kcal/g-
molecule (or perhaps, 263 ltcal/g-molecule). If k = A e-EIRT, then, expressing kl in
(seconds)-', log A = 10.0, or In A = 25.1. This is a somewhat low figure, but not ex-
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ceptionally so. This is for concentrations of hydroxide ion low enough for thein apparently
not to affect the rate to any great extent.
The inechanism of the reaction cannot be deduced with any certainty froin these
results. T h e most plausible suggestion, perhaps, is that the initial, and slowest, stage is a
reaction with \\later:

follo~vedby a more rapid further reaction of H S O c with dithionite ions:

This suggestioil is very tentative. Hoxvever, if it is correct, the reaction is really bimolec-
ular, and ct[S20c-]/dt = -k2[S204--].[I-120]. Allowirlg for the concentration of water,
and if kg = A s e-"IRT, then log A z = 0.2 (time in seconds), a fairly typical figure (7).

DECOMPOSITION OF TI-IE SOLID

I t seeillecl of interest to compare rates in the solid with those in solution, although if
the above suggestion about the nlechanisnl is correct, the reaction inust necessarily go
by a different route in the solid. Finely ground solid (between 100 and 200 mesh) was
used, and the fraction decomposed a t different times is given in Table 11.
These results give typical S-shaped curves when the fraction decon~posed(represented
by a in the equations below) is plotted against time. Various equations have been pro-
posed to explain similar curves for other reactions of solids (e.g. (8)), the different equa-
tions being based on different ~llechanisms.In applying them, there is a difficulty because
the sample took a finite time to come to the tenlperature of the run, and consequently
there is some doubt about the true zero of time for the reaction. T o avoid this difficulty
the lllethod generally adopted was to plot the obsei-ved time to reach a given value of a
against the calculated time to reach the same value. This was done for the range of a
froin 0.1 to 0.95, and a suitable equation should give a straight line for the resulting
graph. Even so the decision between various equations is not too easy, since all give, if
 LISTER A N D GARVIE: SODIUM DITHIONITE 1571

TABLE I1
Decomposition of solid sodium dithionite

Run 1: 155" C

kte
{Time (min)
(min)
30
0038
272
0 772
60
0065
30
0 834
90
0092
333
0 908
120
0.151
362
0 953
150
0230
180
0.355
210
0.458
2-10
0.610

Run 2: 160' C

i:
Time (min) 30 60 93 120 150 165 180 195
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0.081 0.123 0.225 0.366 0.623 0.712 0.798 0.900

Time (min) 210 225
0.941 0.962
Run 3: 165' C
Time (rnin) 15 30 45 60 75 90 107 120
0062 0095 0145 0257 0405 0.563 0.737 0854
135 150 165
0 939 0 983 0 994
Run 4: 170' C
{ T i y (mill) 15 30 45 60 75 90 105
0 076 0 204 0 507 0 741 0 902 0 978 0.989

a is plotted against time, roughly linear middle sections, siinilar to what is found experi-
meiltally; and consequently graphs of calculated against experimental times were always
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linear over a considerable range in the middle. Hence a decision for or against a possible
mechallisin largely depended on the ends of the curves.
The equations quoted by Garner (8) may be divided illto those which take accourlt
of overlap and iilterfereilce between growing reaction zones, and those which do not.
The latter are oilly applicable in the early stages of the reaction, and so cannot be applied
here. On the former, the following deductioils seeill possible.
1. Branching Nuclei, InterJering During Growth
Garner and Hailes (9) suggested that nuclei might iilitially form very rapidly up to a
certain maxin~umnumber, and thereafter illcrease by branching. At the same time
nuclei might disappear as centers of reaction by becoming totally surrounded by reacted
material. The chance of this happening was taken to be proportional to a. If N is the
nuinber of nuclei a t time, t , these assumptioils mean that

where k3 and k4 are constants. If each nucleus grows linearly with time, da/dt = klN,
the nuclei being supposed to grow out in one dimension and not as spheres. Hence the
curve of a against t will have an inflexion a t a = a1 = ka/k4. If N = 0 a t a = 0, these
equations lead to
In [a/(2al- a ) ] = k3t C+
where C is an integration constant.
In the present curves al is about 0.5 (as was found in other cases by Garner and Hailes),
and a plot of In [&/(I-a)] against t was fairly linear. The values of k3 were calculated to
be :
T 155 160 165 170 " C
k3 1.9 3.3 5.4 8.2X10-2 min-l.
These values malte the activation energy for the growth process 36 ltcal/g-molecule.
 1572 CANADIAN JOURNAL O F CHEMISTR\'. VOL. 37. 1959

There is some deviation from this equation if a is small, but in any case the approxinlations
made in deriving it are not valid a t low values of a. This is because the assumption t h a t
N = 0 a t a = 0 is not really correct. If we assume that N = N1, a small number, when
a = 0, the equation becomes:

As a evidently approaches unity a t large values of t, presumably

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Fairly good lines are obtained if Nlkl/kB = 0.04 for all runs; the resulting values of
k3 are:
T 155 160 165 170 " C
k3 2.35 3.65 5 . 6 9.05X10-2 min-l.

These give an activation energy of 34.1 kcal/g-molecule.

2. Random Surface Nucleation Followed by Rapid Surface Growth
Here it is proposed that random nucleation occurs, but once it has occurred on a
grain of the material either the entire surface, or certain faces of it, is rapidly covered
with a reaction zone, which then moves slowly towards the center. If No is the total
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number of grains, and N of these are nucleated, then dN/dt = kl(N0-N). If the re-
action zone moves a t a constant speed, a is given by:

where to is the time any one grain takes to decompose. This is valid up to t = to, as it
does not allow for some grains having totally deconlposed. If t > t o , a is given by:

When these equations were compared with the experimental curves, it was not possible
to get a good fit. In particular they malce a rise much too rapidly a t first as co~upared
with experiment, though this improves somewhat if klto is very large. However, it seelns
unlikely that this is the correct mechanisn~.Other assumptions about the proportion of
the surface nucleated led to modified equations, but none were found to give a good
agreement with experiment.
3. Ralzdom Surface Nucleation, but no Rapid Surface Growth
On this picture nucleation starts a t a point on the surface of the grain, and the reacted
zone spreads inwards like a growing sphere. If each grain is itself spherical, the fraction
of any grain reacting in time, t, is

where t o is the time for any grain to react conlpletely. If nucleation is random the equations
for cu are:
[i] t < to; a = (24A3+72A4)( e ~ ~ l ~-3Uc+4U3+12A
~-l) U3-12AU2-36A2U2
+248W+72A3U

[ii] t > to; a = 1 -e-Ul"[24A3+72A4- (12A2-48A3+72/14) el/"]

where U = t/to and A = l/klto, and kl is the rate constant for the nucleation process.
 LISTER AND GARVIE: SODIUM DITHIONITE 1573

These equations make the rise in a too steep a t first unless klto is fairly large (about 7
or more), under which conditions the rate of nucleation is rapid compared with the time
for a particle to react. However, even if klto is large a plot of U against experimental
times for the same a does not give a good straight line. Hence this is probably not the
correct mechanism.

4. Random Nucleation with Ingestion of Nuclei

Here it is proposed t h a t nuclei are formed a t random throughout the material, and the
radii of the nuclei grow a t a constant rate. Allowance is made for the impingement of the
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nuclei on each other. This leads to the equation:

where u = klt, and kl is the rate constant for nucleation. B is a constant equal to 8nNokz3/
Vok13,where N o is the total number of nuclei, kt is the rate of nucleus growth, and Vo
is the total volume of material (10).
The form of the curves is little altered by changes in B, so t h a t it is not possible t o
deduce the best value of B with any precision. Plots of u against the experimental time
for the same values of a give good lines if B is fairly large (about lo), though the data
for 170" C fit a somewhat smaller value of B (about 2 to 5). If B is 10 a t all temperatures,
values of kl are:
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155 160 165 170 " C

{i 2.55 4.3 7.15 10.2X10-3 minin-l.

This gives a linear plot of log kl against l / T corresponding to an activation energy of

35.7 kcal/g-molecule.
However, B should vary with temperature, and as the activation energy of nucleation
is presumably larger than t h a t of growth, B should fall with increasing temperature.
Different values of B a t 170" C, with B = 10 a t 155' C, give the following activation
energies :
[i;1700ci lo 5 2 1
35.7 39.0 45.4 5 0 . 4 kcal/g-molecule
35.7 33.2 31.9 3 1 . 1 kcal/g-molecule.

Here El is the activation energy of nucleation, and E2 that of growth. If B = 5 a t 170" C,

then kl = 12.0X10-3 min-l; if B = 2, kl = 15.5X min-l, both a t 170" C.
As a general conclusion, this last equation undoubtedly gives the best agreement with
the experimental points, and is somewhat superior to the equation for the branching
mechanism; so probably the correct nlechanisin is one of random nucleation and linear
growth. Although some other mechanisms have been definitely excluded above, one
cannot be certain that some hitherto unsuggested mechanisin might not also fit the
experimental points. Because of the small change in the curves representing random
nucleation and linear growth as B varies, it is not possible to separate all the rate con-
stants, but that for the nucleatioil rate must be approxin~atelyas indicated above. T h e
activation energy for growth is 32 to 33 kcal/g-molecule, while the most that can be
said about the activation energy for nucleation is that it is probably 40 to 45 kcal/g-
molecule. As is to be expected, these are considerably larger than the solution activation
energy of 2 6 i kcal/g-molecule.
 1574 CANADIAN JOURNAL OF CIIEMISTRY. VOL. 37, 1060

REFERENCES
1. JELLINBII,I<. and JELLINEK,
E. Z. physik. Chem. 93, 325 (1919).
2. LANGE,N.A. Handbook of chemistry. Handbook Pubs., Inc., Sandusky, Ohio. 1956. p. 1202.
3. DFIXES,0. and ELSTNER, G. Z. anorg. u. allgem. Chem. 191, 340 (1930).
4. HAIIN,F. L. Anal. Chim. Acta, 3, 62 (1949).
5. HAHN,F. L. Anal. Chim. Acta, 3, 65 (1949).
6. SMITH,J . H. J. Am. Chem. Soc. 43, 1307 (1921).
7. SMITH,J. H. J. Am. Chern. Soc. 43, 76 (1921).
8. GARNER,\V. E. Chenlistry of the solid state. Butterworth Scientific Publications, London. 1955.
Chap. 7.
9. GARKER, W. E. and HAILES,H. R. Proc. Roy. Soc. A, 139, 576 (1933).
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10. AVRAMI,M. J. Chern. Phys. 7, 1103 (1939); 8, 212 (1940).

For personal use only.