The Early Asimov. Volume 1

The Endochronic Properties of Resublimated Thiotimoline

The correlation of the structure of organic molecules with their various properties, physical and chemical, has in recent years afforded much insight into the mechanism of organic reactions, notably in the theories of resonance and mesomer-ism as developed in the last decade. The solubilities of organic compounds in various solvents has become of particular interest in this connection through the recent discovery of the endochronic nature of thiotimoline.

It has been long known that the solubility of organic compounds in polar solvents such as water is enhanced by the presence upon the hydrocarbon nucleus of hydrophilic - i.e., water-loving - groups, such as the hydroxy (-OH), amino (-NH₂), or sulfonic acid (SO₃H) groups. Where the physical characteristics of two given compounds - particularly the degree of subdivision of the material - are equal, then the time of solution - expressed in seconds per gram of material per milli-liter of solvent - decreases with the number of hydrophilic groups present. Catechol, for instance, with two hydroxy groups on the benzene nucleus, dissolves considerably more quickly than does phenol, with only one hydroxy group on the nucleus. Feinschreiber and Hravlek in their studies on the problem have contended that with increasing hydrophilism, the time of solution approaches zero. That this analysis is not entirely correct was shown when it was discovered that the compound thiotimoline will dissolve in water - in the proportions of 1 gm./ml. - in minus 1.12 seconds. That is, it will dissolve before the water is added.

Previous communications from these laboratories indicated thiotimoline to contain at least fourteen hydroxy groups, two amino groups and one sulfonic acid group. The presence of a nitro group (-NO₂) in addition has not yet been confirmed, and no evidence as yet exists as to the nature of the hydrocarbon nucleus, though an at least partly aromatic structure seems certain of solution of thiotimoline quantitatively met with considerable difficulty because of the very negative nature of the value. The fact that the chemical dissolved prior to the addition of the water made the attempt natural to withdraw the water after solution and before addition. This, fortunately for the law of Conservation of Mass-Energy, never succeeded, since solution never took place unless the water was eventually added. The question is, of course, instantly raised as to how the thiotimoline can 'know' in advance whether the water will ultimately be added or not. Though this is not properly within our province as physical chemists, much recent material has been published within the last year upon the psychological and philosophical problems thereby posed.

Nevertheless, the chemical difficulties involved rest in the fact that the time of solution varies enormously with the exact mental state of the experimenter. A period of even slight hesitation in adding the water reduces the negative time of solution, not infrequently wiping it out below the limits of detection. To avoid this, a mechanical device has been constructed, the essential design of which has already been reported in a previous communication.⁶ This device, termed the endochronometer, consists of a cell 2 cubic centimeters in size into which a desired weight of thiotimoline is placed, making certain that a small hollow extension at the bottom of the solution cell - 1 millimeter in internal diameter - is filled. To the cell is attached an automatic pressure micro-pipette containing a specific volume of the solvent concerned. Five seconds after the circuit is closed, this solvent is automatically delivered into the cell containing the thiotimoline. During the time of action, a ray of light is focused upon the small cell-extension described above, and at the instant of solution, the transmission of this light will no longer be impeded by the presence of solid thiotimoline. Both the instant of solution - at which time the transmission of light is recorded by a photoelectric device - and the instant of solvent addition can be determined with an accuracy of better than 0.01 %. If the first value is subtracted from the second, the time of solution (T) can be determined.

The entire process is conducted in a thermostat maintained at 25.00° C. - to an accuracy of 0.01 ° C.

Thiotimoline Purity - The extreme sensitivity of this method highlights the deviations resulting from trifling impurities present in thiotimoline. (Since no method of laboratory synthesis of the substance has been devised, it may be practically obtained only through tedious isolation from its natural source, the bark of the shrub Rosacea Karlsbadensis rugo.) Great efforts were therefore made to purify the material through repeated recrystallizations from conductivity water - twice redistilled in an all-tin apparatus - and through final sublimations. A comparison of the solution times (T) at various stages of the purification process is shown in Table I.

Averaee 'T'

Purification stage (12 obser- 'T' extremes % error

vations)

As isolated -0.72 -0.25; -1.01 34.1

First recrystallization -0.95 -0.84; -1.09 9.8

Second recrystallization -1.05 -0.99; -1.10 4.0

Third recrystallization -1.11 -1.08; -1.13 1.8

Fourth recrystallization -1.12 -1.10; -1.13 1.7

First resublimation -1.12 -1.11; -1.13 0.9

Second resublimation -1.122 -1.12; -1.13 0.7

It is obvious from Table I that for truly quantitative significance, thiotimoline purified as described must be used. After the second resublimation, for instance, the error involved in an even dozen determinations is less than 0.7%, with the extreme values being -1.119 seconds and -1.126 seconds.

In all experiments described subsequently in this study, thiotimoline so purified has been used.

Time of Solution and Volume of Solvent - As would seem reasonable, experiments have shown that increasing the volume of solvent enables the thiotimoline to dissolve more quickly - i.e., with an increasingly negative time of solution. From Figure 1, however, we can see that this increase in endo-chronic properties levels off rapidly after a volume of solvent of approximately 1.25 ml. This interesting plateau effect has appeared with varying volume of solvent for all varieties of solvents used in these laboratories, just as in all cases the time of solution approaches zero with decreasing volume of solvent.

Time of Solution and Concentration of a Given Ion - In Figure 2, the results are given of the effect of the time of solution (T) of varying the volume of solvent, where the solvent consists of varying concentrations of sodium chloride solution. It can be seen that, although in each case the volume at which this plateau is reached differs markedly with the concentration, the heights of the plateau are constant (i.e. -1.13). The volume at which it is reached, hereinafter termed the Plateau Volume (PV), decreases with decreasing concentration of sodium chloride, approaching the PV for water as the NaCl concentration approaches zero. It is, therefore, obvious that a sodium chloride solution of unknown concentration can be quite accurately characterized by the, determination of its PV, where other salts are absent.

This usefulness of PV extends to other ions as well. Figure 3 gives the endochronic curves for 0.001 molar solutions of sodium chloride, sodium bromide and potassium chloride. Here, the PV in each case is equal within the limits of experimental error - since the concentrations in each case are equal - but the Plateau Heights (PH) are different.

A tentative conclusion that might be reached from this experimental data is that the PH is characteristic of the nature of the ions present in solution, whereas the PV is characteristic of the concentration of these ions. Table II gives the values of Plateau Height and Plateau Volume for a wide variety of salts in equal concentrations, when present alone.

The most interesting variation to be noted in Table II is that of the PV with the valence type of the salt present. In the case of salts containing pairs of singly-charged ions - i.e., sodium chloride, potassium chloride and sodium bromide - the PV is constant for all. This holds also for those salts containing one singly charged ion and one double charged ion - i.e. sodium sulphate, calcium chloride and magnesium chloride - where the PV, though equal among the three, varies markedly from those of the first set. The PV is, therefore, apparently a function of the ionic strength of the solution.

This effect also exists in connection with the Plateau Height, though less regularly. In the case of singly charged ions, such as in the first three salts listed in Table II, the PH is fairly close to that of water itself. It falls considerably where doubly charged ions, such as sulphate or calcium, are present. And when the triply charged phosphate ion or ferric ion is present, the value sinks to merely a quarter of its value in water.

Solvent (Salt solutions in Plateau Height Plateau Volume

0- 001 M concentration) (PH) seconds (PV) milliliters

Water -1.13 1.25

Sodium Chloride solution -1.13 1.37

Sodium Bromide Solution -1.10 1.37

Potassium Chloride solution -1.08 1.37

Sodium Sulphate solution -0.72 1.59

Calcium Chloride solution -0.96 1.59

Magnesium Chloride solution -0.85 1.59

Calcium Sulphate solution -0.61 1.72

Sodium Phosphate solution -0.32 1.97

Ferric Chloride solution -0.29 1.99

Time of Solution and Mixtures of Ions - Experiments currently in progress in these laboratories are concerned with the extremely important question of the variation of these endo-chronic properties of thiotimoline in the presence of mixtures of ions. The state of our data at present does not warrant very general conclusions, but even our preliminary work gives hope of the further development of the endochronic methods of analysis. Thus, in Figure 4, we have the endochronic curve where a mixture of 0.001M Sodium Chloride and 0.001M Ferric Chloride solutions is the solvent. Here, two sharp changes in slope can be seen: the first at a solution time of -0.29, and the second at -1.13, these being the PH's characteristic of Fer ric Chloride and Sodium Chloride respectively - see Table II. The PH for a given salt would thus appear not to be affected by the presence of other salts.

This is definitely not the case, however, for the PV, and it is to a quantitative elucidation of the variation of PV with impurities in the solvent that our major efforts are now directed.

Summary - Investigations of the endochronic qualities of thiotimoline have shown that:

a - Careful purification of the material is necessary for obtaining quantitative results.

b - Increasing the volume of solvent results in increasing the negative time of solution to a constant value known as the Plateau Height (PH), at a volume of solvent known as the Plateau Volume (PV).

c - The value of the PH is characteristic of the nature of the ions present in the solvent, varying with the ionic strength of the solution and not varying with the addition of other ions.

d - The value of the PV is characteristic of the concentration of the ions present in the solvent, being constant for different ions in solution of equal ionic strength, but varying markedly with the admixtures of second varieties of ions.

As a result of all this, it is suggested that endochronic methods offer a means of rapid - 2 minutes or less - and accurate - within 0.1 % at least - analysis of inorganic, water-soluble materials.

Bibliography:

P. Krum and L. Eshkin. Journal of Chemical Solubilities, 27, 109-114 (1944), 'Concerning the Anomalous Solubility of Thiotimoline.'

E. J. Feinshreiber and Y. Hravlek. Journal of Chemical Solubilities, 22, 57-68 (1939), 'Solubility Speeds and Hydro-philic Groupings.'

P. Krum, I. Eshkin, and O. Nile. Annals of Synthetic Chemistry, 115, 1122-1145; 1208-1215 (1945), 'Structure of Thiotimoline, Parts I amp; II.'

G. H. Freudler, Journal of Psychochemistry, 2, 476-488 (1945), 'Initiative and Determination: Are They Influenced by Diet? - As tested by Thiotimoline solubility Experiments.'

E. Harley-Short, Philosophical Proceedings amp; Reviews, 15, 125-197 (1946), 'Determinism and Free-Will. The Application of Thiotimoline Solubility to Marxian Dialectic.'

P. Krum, 'Journal of Chemical Solubilities, 29, 818-819 (1946), 'A Device for the Quantitative Measurement of Thiotimoline Solubility Speed.'

A. Roundin, B. Lev, and Y. J. Prutt, Proceedings of the Society of Plant Chemistry, 80, 11-18 (1930), 'Natural Products isolated from shrubs of the genus Rosacea.'

Tiotimolin kak Ispitatel Marksciiskoy dilektiki B. Kreschia-tika, Journal Naouki i Sovetskoy Ticorii Vol. 11, No. 3.

Philossophia Neopredelennosti i Tiotimolin, Molvinski Pog-ost i Z. Brikalo. Mir i Kultura Vol. 2, No. 31.

When Campbell took the piece, I made one cautious stipulation. I knew it would appear in the spring and I knew that in the spring I would come up for my “oral examinations”-the last hurdle on the path to my Ph.D. I didn’t want any austere member of the examining board to decide I was making fun of chemical research and to be sufficiently offended to vote against me on the grounds that I wasn’t temperamentally suited to the high honor of the doctorate. -So I asked Campbell to run it under a pseudonym.

When the magazine with the article finally reached the newsstands, in mid-February 1948, I was appalled to discover that Campbell had utterly forgotten the matter of the pseudonym. The article appeared under my own name and I was scheduled to have my orals within three months. My nervousness was increased when, almost at once, copies of the magazine began circulating in the chemistry department.

On May 20, 1948, I had my orals. The examining board had seen the article. After I had been on the grill for an hour and twenty minutes, the last question (asked by Professor Ralph S. Halford) was, “Mr. Asimov, tell us something about the thermodynamic properties of the compound thiotimoline.”

I broke into hysterical laughter out of sheer relief, for it struck me instantly that they wouldn’t play good-natured jokes with me (Professor Halford sounded jovial and everyone else was smiling) if they were going to Hunk me. I was led out, still laughing, and after a twenty-minute wait, the examiners emerged, shook my hand, and said, “Congratulations, Dr. Asimov.”

My fellow students insisted on forcing five Manhattans down my throat that afternoon and, since I am a teetotaler under normal conditions and have no tolerance for alcohol, I was royally drunk at once. It took them three hours to sober me up.

After the official ceremonies, on June I, 1948, I was Isaac Asimov, Ph.D.

As it turned out, Campbell’s non-use of a pseudonym (and I bet he did it deliberately, because he was smarter than I was) was a lucky break indeed. Not only did the examining board not take it amiss, but the article became, in a minor way, famous, and I with it.

Although “Thiotimoline” appeared in Astounding, as did all my stories of the time, it received circulation far outside the ordinary science fiction world. It passed from chemist to chemist, by way of the magazine itself, or by reprints in small trade journals, or by copies pirated and mimeographed, even by word of mouth. People who had never heard of me at all as a science fiction writer, heard of thiotimoline. It was the very first time my fame transcended the field.

What’s more, although “Thiotimoline” was essentially a work of fantasy, the form was that of non-fiction. Viewed from that standpoint, “Thiotimoline” was the first piece of non-fiction I had ever published professionally-the harbinger of a vast amount to come.

But what amused me most was that a surprising number of readers actually took the article seriously. I was told that in the weeks after its appearance the librarians at the New York Public Library were driven out of their minds by hordes of eager youngsters who demanded to see copies of the fake journals I had used as pseudo references.

But back to the summer of 1947-

Over a period of five years I had sold fourteen stories, every one of them to Campbell. This didn’t mean that he was the only editor in the field, at all. Almost all the magazines that had been published before the war still existed (although only Astounding was really doing well) and would have welcomed submissions from me. Had Campbell rejected any of the stories I had submitted to him, I would certainly have tried one of those other magazines.-but he didn’t, so I didn’t.

The magazine Startling Stories, in which I had published “Christmas on Ganymede” five and a half years before, published a forty thousand-word “short novel” in each issue. It wasn’t easy to get a publishable story of that length every month though, especially since Startling’s rate was only half that of Astounding.

Sometimes it was necessary, therefore, for the editor of the magazine, who at that time was Sam Merwin, Jr., to canvass those authors known to be capable of turning out such a story. About the time I was doing “Thiotimoline,” Merwin approached me with a suggestion that I write a lead short novel.

Startling, he explained, had always published stories with the accent on adventure, but, in imitation of Astounding’s success, he had persuaded the publisher to try the experiment of publishing stories with a heavier accent on science. Would I consider, then, doing a lead for Startling?

I was terribly flattered. Also, as I said earlier, I was nervous about having become a one-editor author and would have welcomed a chance to prove to myself that I could write beyond Campbell’s protective shadow. I agreed, therefore, and a good part of the summer of 1947 (when I wasn’t engaged in preparing my experimental data for the upcoming Ph.D. dissertation) was spent in preparing a story I called “Grow Old with Me.” [This was inspired by Robert Browning’s poem Rabbi Ben Ezra and was a misquotation-which shows you the level of my culture. The first line of the poem is “Grow old along with me.”]

By August 3 I had completed first draft. On August 26, I had the first part of it in final copy and submitted that to Merwin. He approved. On September 23 the entire story was submitted and I had no doubt, whatever, of its acceptance. On October 15, 1947, however, Merwin told me that, alas, Startling had decided not to go for heavy science, after all, but for adventure, and that “Grow Old with Me” would have to be completely rewritten with no guarantee of acceptance after that.

I suppose it is an indication of how things had advanced when I tell you it was the first time that I did not accept a request for revision philosophically. Quite otherwise! It had been five years and more since even Campbell had rejected one of my stories; how, then, dare a comparative nonentity like Merwin do so? Particularly since he had approached me for the story?

I made no effort to hide my annoyance. In fact, I seized the manuscript and stalked out of the office, and in an obvious rage. [Years afterward, as a result of the subsequent history of that story, Merwin took to apologizing for that rejection every time he met me-but he didn’t have to, and I kept telling him so. He was editor, and he was completely within his rights to reject the story, and I was being pettily temperamental to be angry about it. I have made every effort, since, to avoid evident anger at any rejection, however unjustified it might seem at the time, and I think I have succeeded.] I submitted the story to Campbell, giving him a full account of events. -I have always made it a practice to tell any editor to whom I submit a story of any rejection it has previously received. There is no necessity to do this; it is not, as far as I know, an ethical requirement for a writer. I just do it, and it has not, again as far as I know, ever cost me an acceptance.

As it happened, Campbell rejected the story, but not, I’m sure, because it had been somewhere else first. He told me enough things wrong with the story to make me feel that perhaps Merwin had not been so arbitrary in rejecting it. I thrust the story in the drawer in disgust and thought no more about it for nearly two years.

The rejection came at a bad time. More and more, I was wrapped up in trying to complete my research, in writing my dissertation, and, most of all, in anxiously looking for a job. There wasn’t much time to write, and the rejection had sufficiently disheartened and humiliated me so that I withdrew from writing for nearly a year. This was the third long withdrawal of my writing career, and, to this date, the last.

I did not find a job; my expected Ph.D. degree was no passport to affluence, after all. That was humiliating, too.

I accepted an offer from Professor Robert C. Elderfield to do a year’s postdoctoral research for him for $4,500, working on anti-malarial drugs. I accepted, though not with great enthusiasm, and started work for him on June 2, 1948, the day after I had officially gained my Ph.D.-At least it would give me another year to find a job.

By the next month, I had settled down sufficiently to consider writing a science fiction story, “The Red Queen’s Race.” On July 12 it was finished and I submitted it to Campbell. It was accepted on the sixteenth and once again I was back in business.