1994 CAhTADI.4N JOURNAL O F CFIEMISTRY. VOL.

4-1, 1966

According to Bjerrum (3), log T is proportional to elez, where el and e2 are the ionic
charges on the ligands. IHence, Put= bu:bt(calcd.) = 6/5 X 1.6" 3.1, \\-hereas the ob-
served ratio is 2.7.
Stepwise stability constants for three stages of Fe3 +-C1- association have been re-
ported by Rabinowitch and Stoclc~nayer(6) and Olerup (7). The bl:bz values (3.2 and
2.9) are in agreement with Lister and Rivington's (3). The P23(ob~.) values of the two
investigations differ, however. Rabinowitch and Stockinayer (6) report a Pz3value = 32
and Olerup (7) reports a value of 2.3. If the 1:3 chloride complex is octahedral, Pz3(calcd.)
= 3/2 X 5/4 X 1.6 = 2.8, a value in agreement with Olerup's determination. If Rabino-
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witch and Stoclcmayer's (6) P23(0bs.) value is indicative of a change in coordination

from 6 to 4 in the second association stage, then Plz(obs.) would be considerably s~llaller
than calculated; and yet the observed and calculated Plz values are in good agreement.
Olerup's Pzj(obs.) value would therefore seem to be the better.
I t \\-ould appear froin our treatment that the complexes FeC12+, FeSCNClz, and
FeS04.HS04 are octahedral. Olerup's (7) P?3(obs.) value suggests that FeC13 is also
octahedral. I t is lilcely that the transition fro111 six- to four-coordination occurs in either
the third or fourth association stage, probably the fourth.
I t is of interest to note that Gamlen and Jordan (8) concluded from a comparison of
Plz, P 2 3 , and Ps4values that the structural change occurred in the fourth chloride as-
sociation stage. These workers used Rabino\\-itch and Stockmayer's (6) b l and bz values
together with their o\\-11b3 and b4 figures. The TIz and Tz3correlated reasonably \veil, but
For personal use only.

the T34 was extremely high.

1. H. L. FBIEDNAN. J. Am. Chem. Soc. 74, 5 (195'3).

2. STABILITY CONSTANTS OF METAL-ION COJIPLESES. The Chemical Society, London. 1964.
3. b,I. \V. LISTERand D. E. RIVINGTON. Can. J . Chem. 33, 1603 (1955).
4. P. G. MAXNIXG. Can. J. Chem. 43, 3358 (1965).
5. N. BJERRUM. Z. Physili. Chem. Leipzig, 106, 238 (1923).
c. E. RAB~NOWITCH
i . H. OLERUP.
and W. 1-1. STOCK>~AYER. J. Am. Chem. Soc. 64, 335 (1943).
Sverlsli Kern. Tidslir. 55, 324 (1943).
8. G. A. GAIILES and D. 0 . JORDAN. J. Chem. Soc. 1435 (1943).

PREPARATION OF FREMY'S SALT, POTASSIUM NITROSODISULFONATE

This note describes an improved method for the preparation of a stable Fremy's salt,
Kz[ON(S03)2],which has been used as an analytical tool for estimating free phenolic
hydroxyl groups in isolated lignin (I) and also in lignins present in groundurood pulp
(2, 3). The usual methods (4-10) for its preparation consisted essentially in preparing
the sodium or potassium salts of hydroxylainine disulfonic acid follo\ved by oxidation
with either lead oxide, silver oxide, or potassium perinanganate. Fren~y'ssalt prepared
from this material is Icnou-n to be unstable, and the degree of instability has often been
Canadian Jour~lalof Chemistry. Volume 4-1 (1906)
 NOTES 1995

attributed to the method of preparation, to the pI-I of solution, and also t o the presence
of other ions, particularly manganese and chloride, in solution (6).
A method claiming a pure product in high yield was patented by Teuber ( 8 ) and we
have found in our laboratory that certain modifications of Teuber's process produce a
Inore stable product. Teuber's process involves
(a) reaction of sodium nitrite, acetic acid, and sodium bisulfite t o form hydroxylamine
disulfonate, HON (SO&a):,
(b) oxidative dehydrogenation of the product in a with potassiunl permangallate in
the presence of ammonia,
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(c) separation of the reduction product, manganese dioxide, from the salt solution by
repeated filtration, and
(d) crystallization of potassiunl nitrosodisulfonate, 0 K ( S 0 3 1 i ) ? , by addition of the
filtrate t o a saturated solution of potassium chloride, and separation of the crystals
by filtration.
Laboratory experiments sho~vedthat severe decomposition can occur during steps
a -r d. The following modifications \\-ere introduced which resulted in ~narltedimprove-
ment in yields and reproducibility; (i) hydroxylamine disulfonate in step a n-as prepared
fro111 sodium nitrite, sodium bicarbonate, and sulfur dioxide; (ii) the deco~npositionin
step b was minimized by maintaining better pI-I control; (iii) separation of manganese
dioxide by centrifugation before filtration in step c largely prevented decomposition and
resulted in higher yield of the product; (iv) the final product in step d Ivas collected by
For personal use only.

centrifugation and rapidly treated with potassium hydroxide. This again prevented
decomposition in the final stage of preparation and resulted in simplicity of operation.
The solid salt has a yelloxv-orange color and gives purple solutions, which can easily be
analyzed calorimetrically, since their absorptions in the 545 1np region are directly
proportional t o their conce~ltrationsas measured both by weighing of the orange dimeric
solid and by iodine-thiosulfate titration. Solutions in which some deco~npositionhas
occurred call still be estimated colorinzetrically, though not titrimetrically, since hydrolysis
products then interfere. Spectrometric analysis of the salt, obtained by the above method,
showed the follonjing traces of impurities.

The product thus obtained could be stored in the cold for several months xvithout
decomposition.
EXPERIMENTAL*
Potassiz~vziVitrosodiszllfonate
In a 3 1 beaker containing distilled water (250 ml) and crushed ice (500 g) were placed 39.6 g of s o d i ~ ~ ~ n
bicarbonate and 33.0 g of sodium nitrite. T h e mixture was thoroughly mixed with a mechanical stirrer
and was externally cooled to -5' by a freezing mixture of salt and ice. Sulfur dioxide was then passed in
rapidly, and the temperature of the solution was controlled a t -5' to -3'. When the PI-I of the mixture
fell to 2 (approx. 30 min) and the color changed to orange brown, the passage of sulfur dioxide was imme-
diately stopped. T h e mixture was stirred for an additional 10 min, during which time it became colorless.
*Reagent grade cltetnicals were used ilt tlze entire experiwzent.
 1996 CANADIAN JOURNAL OF CHEMISTRY. VOL. 44. 1966

Clean filtered air was then bubbled though the solution for 5 min and the pH of the solution was adjusted
to 10.1 with 18% amnmoniurn hydroxide (approx. 10 ml). The solution was stirred a t -2' for 30 min and
380 rnl of 1 N potassium permanganate cooled a t -3O was then added to it portion-wise a t a rate which
did not allow the temperature to rise above 5". The contents were stirred for 1 h and then allowed t o stand
a t the same temperature. The dark-brown slurry was centrifuged a t 1 950 rpm for 5 min and the supernatant
violet liquid was passed through a filter paper into a saturated solution of potassiun~chloride (250 g in
700 ml water a t 30°). On cooling, the solution yielded an orange crystalline precipitate which was collected
by centrifugation. The material was recrystallized from 1 N potassium hydroxide, washed with pure
methanol until free from alkali, and stored in vacuum over P?Oj in a cold room. The yield of the product
was 77.6y0, based on sodium bicarbonate.
Anal. Calcd. for I<?NS207: S, 23.90; I<, 29.14. Found: S, 23.90; K , 29.38.
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ACKNOWLEDGMENTS
The author wishes to acknowledge the assistance of Mr. P. J. DesRosiers in the experi-
mental work, and Dr. R. R. Barefoot for conducting the trace illeta1 analysis.

1. E . ADLERand I<. RUNDQUIST.Acta Chem. Scand. 15, 233 (1961).

2. D. H. ANDKEWS and P. J. DESROSIERS. Pulp Paper Mag. Can. 67, T-119 (1966).
3. R. P. SINGH. Tappi. In press.
4. R. ASMUSSEN. Z. Anorg. Chem. 212, 317 (1933).
5. J. W. MELLOR. Inorga~licchemistry. Vol. VII I. p. 672 ff.
6. J. H. MURIBand D. M. RITTER. J . Am. Chern. Soc. 74, 3394 (1952).
7. G. HARVEY and R. G. W. HOLLINGSHED.Chem. Ind. London. 244 (1953).
8. H. J. TEUBER. Ger. Patent No. 942,562 (May 3 , 1956) ; U.S. patent h o . 2,752,210 (February 19,
1957) ; U.S. Patent No. 2,89?,052 (July 28, 1959).
9. W. G. PALMER. Experimental ~norganicchemistry. Cambridge University Press, London. 1954. p. 281.
10. C. SALTand M. '~OMLINSON. C h e i . Ind. Londo~l,549 ( 1 9 a ) .
For personal use only.