COMPARISON OF THE ACIDITY OF VERY WEAK ACIDS

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000600310159-1
• Release Decision: RIPPUB
• Original Classification: S
• Document Page Count: 4
• Document Creation Date: December 22, 2016
• Document Release Date: August 12, 2011
• Sequence Number: 159
• Publication Date: May 17, 1950
• Content Type: REPORT

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"~... FAR OFFICIAL l1~E
FOREIGN DOCUMENTS OR RADIO ~R U~14Oy
I`~ '"u l' ~ u
COUNTRY USSR DATE OF
~UL 2 9 ~~3AINFORMATION
SUBJECT Scientific - Chemistry, deuterium
_AR Ap?I~I., u~~ O Y
HOW DAT DIST. ~ May 1950
PUBLISHED Thrice-monthly periodical
DATE
PUBLISHED 21 Feb 1950
SUPPLEMENT TO
LANGUAGE Russian REPORT NO.
TNI! OOCU Y[NT CONTAII~i IX iONY ATION AiiECTING TNf NATIONAL O[i[XS[
Oi TNL UNITED STATFS WITHIN TN[ MEANING Oi ESPIONAGE ACT GO
V. S- C., ]1 ANO ]L. AS AYFNOE O. ITS TPANlYISlION OP TN[ N[TFLATIOM
Oi IT! CONTENTS IN ANT YAM NFN TO AN UNAVTNO PIIEO PFPlON I! PNO~
NIYITEO BT LAW. Y[PNODUCTION Oi TNI! TONY IS PPONIOIT[D.
SOURCE Doklady Akademii Nauk SSSR, New Series, Vol LXX, No 6, 1950.
By A. I. Shatenshteyn
Submitted 24 October 1949
Presented by Academician N. N. Semenov 30 November 1949
~A Digest.7
Using the protophilic properties of liquid ammonia, the acidity of weak
acids like acetamide and urea could be determined by the author(1). The under-
lying principle can also be used to determine hydrogen mobility in hydrocarbons
and other substances which, from the chemical point of view, function as acids
in orgatrometallic compounds(2). Using deuteroa:Lvmonia as a solvent, the proton?
of the solute carp be considerably loosened, and exchange of the proton for 'g-'"'
deuteron effected. C-A groups which do not readily enter into an exchange re-
action with heavy water or deuteroalcohol, even in the presence of alkali (4,6),
can be easily brought into reaction with deuteroammonia, particularly in the
presence of potASSium amide ( ^~ 0.25N). Then the differences .in exchange re-
action rates are especially pronounced, so that a quantitative comparison of the
mobility of hydrogen and its capacity for ionization in compounds where the hy-
drogen does not have much mobility becomes possible(5).
The two appended tables show results ob,ained by the author for a number of
compounds. In Table 1, d? is the coefficient of the distribution of deuterium
between the organic substance and the solvent and n the number of atoms of hydro-
gen exchanged for deuterium. The results in Table 2 were calculated according
to the formula pln = N -~ , where N is the total number of hydrogen atoms in
the organic compound, c the co;~centration of deuterium in the water resulting
from the combustion of the compound after exchange, and c, the concentration oY
deuterium in deuteroammonia. The rate constant was calculated according to the
equation fo* a monomolecular react?cn. The values of d?n were determined experi-
mentally in the cases of indene and acetoph~none ( DC n = 2.4), and also for fluo-
rene ( ch n = 1.7). For all other substances it was arbitrarily assumed that
(d~ n)~ = 1. Shown in parentheses are values of the rate constant which have
been calculated for the purpose of orientation on the basis of a proximate value
FOR OFFICIAL RAF OI~L1l
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-,
for the energy of activation. Along with the rate constants for the reaction
of isotope exchange, Table~'~2 lists conventional constants of ionization
(PK . -1gK).
It is known that hydrn bound to oxygen or nitrogen enters into an ex-
change reaction instantanebus~y even in heavy water. Consequently, the method
of isotope exchange cannot contribute anything of value as far as the compari-
son of hydrogen mobilities in compounds of this type is concerned. According
to A. I. Brodskiy (5), this is die to the presence bf a free pair of electrons
in nitrogen or oxygen. Deuterium combines with the electron pair and a proton
is simultaneously split off. On the other hand, a deuteron can combine with a
carbon atom only after the hydrogen bound to the latter has been ionized. This
is a process which requires an exrenditure of activation energy. The reaction
rate will be higher when the hydrogen passes into the ionic state more easily.
In other words, there is a parallelism between the reaction rate constants and
the ionization constants.
Using liquid ammonia in which potassium amide had been dissolved, all hy-
drogen atoms of naphthalene could be replaced with deuterium. Similarly, hy-
drogen atoms of the methyl group of toluene could be replaced and exchange re-
actions with other compounds having a low r?obility of hydrogen carried out.
.l. A. I. Shatenshteyn, Theory of AciSis and Bases, 1949
~r
2. 3C. A. Kocheshkov and T. V. Talalayeva, Synthetic Methods in the Field
of Organometallic Compounds, issue No 1, 1949
3. J. B. Conznt and G. W. Wheland, J. Am. Chem. S., Vol LIV, p 1212,
1932; i1. K. McEwen, ibid, Vol LVIII, p 1124, 1936
6. M. Kharash, W. Brown, and J. McNab, J. Org. Chem., Vol II, p 36, 1937
Tables follow?
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 Sanitized Copy Approved for Release 2011/08/17 :CIA-RDP80-00809A000600310159-1
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Table 2. Constants of Isotope Exchange Reaction Rates in ?euteroammonia* and
Conventional Ionization Cons'.tants of Weak Acids
1
Ionization Constant
Substance Rate Constant (min -
)
pK -
-1gK
k2~o ~
k120?
Data from
Conant and
Wheland
(3~
Data from
McEwen
(3)
Methyl alcohol Instantaneous -
-
-
16
Diphenylamine -
-
-
23
p-Toluidine -
-
_
27
Indene 1 X 10-3 -
(6 X 10-1)
22
~1
Acetophenone 3 X 10-4 -
-
20
19
Fluorene 4 X 10-5 2 X 10-~
(1 X 10-2)
24
25
m-Dinitrobenzene - 2 X 10-5
-
-
-
p-Plitrotoluene 1 X 10-6 4 X 10-6
6 X 10"~
-
-
dl- Picoline - _
2 )C 10-5
-
-
.~uinal.dine - -
1 X10-5
-
-
Tri_~hcnyl*~ethane - -
2 X 10-6
28.5
33
Acenaphthene - -
2 X 10'6
-
-
Naphthelene - -
6 X 10-6
-
-
Sodium formiate - -
6 X 10"7
-
-
Sodium acetate - -
4 X 10-7
-
-
Diphenylmethane - -
3 X 10-7
29.5
35
*`!.'he values of rate constants determined in the present investigation and
listed here are purely for the purpose of comparison and orientation.
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