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NBS MONOGRAPH 34

Tables of Chemical Kinetics


Homogeneous Reactions
(Supplementary Tables)

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NATIONAL BUREAU OF STANDARDS
Tables of Chemical Kinetics
Homogeneous Reactions
(Supplementary Tablet)

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Each table is designated by a six-digit number, the first two of which refer to the
type of reaction, the third to the phase of the homogeneous reaction, gaseous (1), liquid
(2), or solid (3). The indication of the phase is repeated at the upper right-hand
corner of the first sheet of each table. The second three-digit group of the table number
refers io the types of substances involved. Within each table, reactions are numbered.
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UNITED STATES DEPARTMENT OF COMMERCE Luther H. Hodges, Secretary
NATIONAL BUREAU OF STANDARDS A. V. Astin, Director

Tables of Chemical Kinetics


Homogeneous Reactions
(Supplementary Tables)

National Bureau of Standards


A. V. Astin, Director

National Research Council, Division of Chemistry


Committee on Kinetics of Chemical Reactions
M. L. Kilpatrick, Chairman
J. Bigeleisen H. Taube
R. Noyes K. Wiberg
C. Satterfield

Project Office: Hepburn Hall, St. Lawrence University, Canton, Naw York
C. H. Stauffer, Project Director
A. R. Amell D. M. Kern
E. Buncel H. G. Kuivila
T. W. Davis P. E. Merritt
J. O. Edwards M. Szwarc
H. B. Feldman H. Taube
C. L. Gage M. H. J. Wijnen
H. S. Johnston

National Bureau of Standards Monograph 34


To Accompany National Bureau of Standards CSIO, Supplements 1 and 2
Issued September 15,1961
Contents
(Supplementary Tables)
Pag*
Preface.______-_-------------_----_-_--___-_--__---_---__--__--__--_-- iii
Subject index_______-___-_____________________ __________-____.____-___ iv
Tables...--___--_---_--____---_-_---___---_---_-------___--____-_--_-- 1

ii
SUPPLEMENT 3 TO TABLES OF
CHEMICAL KINETICS
HOMOGENEOUS REACTIONS

PREFACE

A description of these Tables and definition of the terms and abbreviations used may be
found In the Introduction to the 1951 publication. A brief description of the method used in
compiling these tables and the limitation of coverage is given in the preface to Supplement 1.
A description of the numbering system used in classifying reactions for the tables is given in
Supplement 2. The present supplement contains information pertaining to Substitution, Exchange
and Elimination reaction types. It is not complete as still more material falling in these groups
is being prepared. The amount of kinetic data to be studied made It seem advisable to present
all the material completed to date without further delay. The date on each section gives the year
and month to which the literature had been surveyed. Significant omissions or errors should be
reported to Dr. Charles H. Stauffer, Head, Department of Chemistry, St* Lawrence University,
Canton, New York.

The Director and his associates gratefully acknowledge the financial assistance provided by
the Office of Ordnance Research, Department of the Army which made this work possible. The Di
rector of the Project gratefully acknowledges the able assistance of his associates and collab
orators, the help of the National Bureau of Standards, the National Academy of Sciences and the
members of the Committee on Chemical Kinetics of N. R. C. Division of Chemistry-

C.H. Stauffer

National Bureau of Standards - National Research Council December, 1959

in
Homogeneous Reaction Kinetics

SUBJECT INDEX
Table
3oo EXCHANGE-SUBSTITUTION , mie of Tabl \
(number of pages) number

300 ISOTOPIC EXCHANGE


301 Isotopic exchange (gas)
Isotoplc exchange; hydrogen exchange on
aliphatic C (2) 301.401
Isotoplc exchange; oxide of carbon (2) 301.464
Isotoplc exchange; halogen on aliphatic C (4) 301.471
Isotoplc exchange; halogen In IVth group
hallde (l) 301.474
Isotoplc exchange; oxides of nitrogen (1) 301.565
Isotoplc exchange; hydro gen- hydro gen hallde (1) 301.701
Isotoplc exchange; halogen-halogen hallde (3) 301.770

302 I so topic exchange (liquid}


Isotoplc exchange; ammonia famine) complex
on group I element (l) 302.150
Isotoplc exchange; halogen complex on
group I element (l) 302. 170
Isotoplc exchange; valence state group I
ions (l) 302. 190
Isotopic exchange; cyanide complex group II
element (2) 302.240
Isotopic exchange; valence state group III
ions (11) 302.390
Isotopic exchange; H-D, (T) exchange on
aliphatic C (12) 302.401
Isotopic exchange; H-D, exchange on
aromatic C (10) 302.402
Isotoplc exchange; H-D exchange on C in
heterocycllc ring (l) 302.403
Isotopic exchange; oxygen isotope exchange
on carbon (6) 302.461
Isotopic exchange; sulfur exchange between
disulfide and thlol (2) 302.466
Isotoplc exchange; halogen on IVth group
halide (l) 302.474
Isotoplc exchange; halogen for halogen in
organic compounds (23) 302.477
Isotoplc exchange; hydrogen isotope exchange
between Vth group element and H-0 bond (3) 302.506
Isotoplc exchange; hydrogen isotope exchange
on N in VI 11th group complex (l) 302.508
Isotoplc exchange; hydrogen isotope exchange
on N with molecular hydrogen (l) 302.511

National Bureau of Standards - National Research Council December, 1959

IV
Homogeneous Reaction Kinetics

SUBJECT INDEX (continued)

310 HYDROGEN SUBSTITUTION Title of Table Table


(number of pages) number
311 Hydrogen substitution (gas)
Hydrogen substitution; halogen replaced by H
on aliphatic C (4) 311.417
Hydrogen substitution; H replaced by halogen
on aliphatic C (4) 311.471
Hydrogen substitution; hydro gen-cyanogen (2) 311.540

312 Hydrogen substitution (liquid)


Hydrogen substitution; H on aliphatic C
with group II metal (2) 312.421
Hydrogen substitution; H of aromatic compound
with group II metal (8) 312.422
Hydrogen substitution; nitration of aliphatic
compounds (l) 312.451
Hydrogen substitution; nitration of aromatic
compounds (22) 312.452
Hydrogen substitution; aryl hydrogen sub-
stlt?ution by azo (Dlazonlum coupling) (15) 312.455
Hydrogen substitution; sulfonation of
aromatic compounds (7) 312.462
Hydrogen substitution; aryl sulfone
formation (2) 312.467
Hydrogen substitution; H by halogen on
aliphatic C (21) 312.471
Hydrogen substitution; H by halogen on
aromatic C (50) 312.472
Hydrogen substitution; H by halogen on
heterocycllc ring (3) 312.473
Hydrogen substitution; replacement of H
by halogen on Si (4) 312.474
Hydrogen substitution; H by halogen on
NH 3 or amine (3) 312.570
Hydrogen substitution; H by halogen on N
in amide (3) 312.571

330 EXCHANGE OF SUBSTITUENTS


331 Exchange of substituents (gas)
Exchange of substituents; replacement of
halogen by NHg and :NH (l) 331.754

332 Exchange of substituents (liquid)


Exchange of substituents; alkali metal
replaced by C (3) 332.141

National Bureau of Standards - National Research Council December, 1959

V
Homogeneous Reaction Kinetics

SUBJECT INDEX

330 EXCHANGE OF SUBSTITUENTS , Title f TaMe . Tab ' e


(number of pages) number
(continued)
332 Exchange of substituents (liquid)
Exchange of substituents; replacement of
Boron by 0 on aromatic C (3) 332.363
Exchange of substituents; replacement of
Boron by halogen on aromatic C (6) 332.^73
Exchange of substituents; replacement of
C by N on aromatic C (3) 332.452
Exchange of substituents; replacement of
C by sulfate on Si (1) 332.464
Exchange of substituents; replacement of
C by halogen on aromatic C (2) 332.472
Exchange of substituents; replacement of
Si by halogen on aromatic C (l) 332.473
Exchange of substituents; replacement of N by
0 on aliphatic C (2) 332.501
Exchange of substituents; replacement of N= by
0= on aromatic C (6) 332.503
Exchange of substituents; replacement of
Ar(SOJ,
o
(ArSOj,
*
(ArSO) by NR'R"R"f (2) 332.653
Exchange of substituents; replacement of
halogen by C (of enolate) (2) 332.741
Exchange of substituents; replacement of
halogen on Si by C (2) 332.744
Exchange of substituents; replacement of
halogen by N0 2 and (or) ONO on aliphatic C (4) 332.750
Exchange of substituents; replacement of
halogen by NO 3" (3) 332.751
Exchange of substituents; replacement of
halogen by azlde (2) 332.753
Exchange of substituents; replacement of
halogen by NH2 and :NH (l) 332.754
Exchange of substituents; replacement of
halogen by S 2 0 3= (15) 332.761
Exchange of substituents; replacement of
halogen by Thlo alkyl (aiyl) (s) 332.763
Exchange of substituents; replacement of
halogen by thlocyanate (2) 332.765
Exchange of substituents; replacement of
halogen by S of thlourea (2) 332.766
Exchange of substituents; halogen for halogen
on aliphatic carbon (34) 332.771

National Bureau of Standards - National Research Council December, 1959

VI
Homogeneous Reaction Kinetics

SUBJECT INDEX (continued)

350 EXCHANGE ON Vth GROUP ELEMENT , Title f Table , Tab l *


(number of pages) number
(continued)
352 Exchange on Vth group element (liquid)
Exchange on Vth group element; halogen replaced
by nitrogen on P (2) 352.750
Exchange on Vth group elemenu halogen for
halogen on P (l) 352.770

4oo ELIMINATION
400 PROTON ELIMINATION
402 Proton elimination (liquid)
Proton elimination; from CH bond activated
by adjacent CO* (COOR), (CN), (N0 2 ) (e) 402.450
420 BOND-UNSATURATIOfJ ELIMINATION
422 Bond-unsaturation elimination (liquid)
Bond-unsaturation elimination; of C RH5N and H*
to form C:C (l) 422.450
Bond-unsaturation elimination; of HNO g and (or)
HN0 2 from nitrate ester (9) 422.451
Bond-unsaturation elimination; of N0 3" and
halidc ion to form C: C (1) 422.457
Bond-unsaturation elimination; thio ether and
H+ from alkyl sulfonium ion (5) 422.461
Bond-unsaturation elimination; aryl sulfonic
acid from alkyl arylsulfonate (10) 422.463
Bond-unsaturation elimination; ArSO g~ and
halide ion to form C:C (1) 422.467
Bond-unsaturation elimination; hydrogen
halide to form C:C (41) 422.471
Bond-unsaturation elimination; halogen
molecule by halide ion (15) 422.477
430 RING-CLOSURE ELIMINATION
432 Ring-closure elimination (liquid)
Ring-closure elimination; C0 3= from
dicarboxylate (2) 432.404
Ring-closure elimination; of Hgo or ROH (6) 432.441
Ring-closure elimination; of H go with
formation of aromatic ring (2) 432.442
Ring-closure elimination; of N0 g" (l) 432.455
Ring-closure elimination; of halogen from
halo thio ether (l) 432.476

National Bureau of Standards - National Research Council December, 1959

VII
Homogeneous Reaction Kinetics

SUBJECT INDEX (continued}

450 ELIMINATION FROM Vth GROUP ELEMENT Title of Table Table


(number of pages) number
(continued}
452 Elimination from Vth group element (liquid}
Elimination from Vth group element; carbonium
Ion from quaternary ammonium salt (l) 452.474
460 ELIMINATION FROM FUNCTIONAL GROUP
it62 Elimination from functional group (liquid)
Elimination from functional group; N 2o from
acl form of nitro alkane (l) 46E.451

National Bureau of Standards - National Research Council


December, 1959
vni
Homogeneous Reactions ISOTOPIC EXCHANGE Gas phase
301.401
Hydrogen exchange on aliphatic C Amounts are In M/ I.
Rate constants are
In M/I and sec.
Rates are In gram
R listed under mass action law indicates quantity listed under k Is rate of reaction not rate constant.
atoms/I and sec.

<D ~10n
k A <D
10n (0 L.
-H A X
Amount of Defined mass- C
No. React! on V_ S 0 (0
reactant 0 i.
act Ion 1 aw Cu
i 0
A 0 +*
E h n n o
o
H- -J

.1 C H + D > CHD, CHD, CHD,CH,H, HD A = B ~ 1.8 x icf 3 dL/dt = R 569 2.4 -7 * ( 8)


24 2 2325 242 26 2
598 5.8 -7
(A) (B) (L) (M) (N) (0) (P) (Q)
616 1.22 -6
643 4.0 -6
662 6.4 -6 57
dM/d = R 569 1.6 -7
598 3.9 -7
616 4.7 -7
643 8.9 -7
662 1.3 -6 35
dQ/dt = R 569 1.0 -7
598 2.7 -7
616 5.4 -7
643 1.8 -6
662 3.4 -6 61
-dA/dt = R 569 4.1 -7
598 1.3 -6
616 2.0 -6
643 4.7 -6
662 9.9 -6 52
.2 CgH^Br + DBr > C 2H 4DBr + HBr 10 3A = 2-24; feAB 258 7.2 -10 (i)
*
10 3B = 1-12 306 1.7 -8 40 2 7

National Bureau of Standards ~ National Research Council


December, 1958
Homogeneous Reaction Kinetics
301.401

COMMENTS
Reaction: (.1) Selected data. Complex chain reaction Involves both exchange and addition. Authors list 14 reactions as
contributing to mechanism. Determined rates of formation of all six products listed and both reactants. Units converted
from molecules cc." * mln" 1 . (.2) Data erratic and results give only order of magnitude. Reaction partially hetero
geneous, air and Br accelerate exchange and Hg Inhibits exchange.

LITERATURE
J.B. Perl, F. Daniels, ACS 1950, 72, 424. ( 8) R.E. Varnerln, J. S. Doollng, ACS 1956, 78, 1119.

National Bureau of Standards - National Research Council


December, 1958
Homog into iii Rtict ioni ISOTOPE EXCHANGE Gas phase
301.464 Oxides of carbon Amounts are i n M/I
unless stated other-
wi se.
Rate constants are i n
M/ | and sec.

k =
o 0)
k x I0n A V.
^ 3 D
Amount of Amount of Def i ned mass c *->
ctf o CtJ
0 S
No, Reaction Addend 6 CO
o. e O
re act ant addend act i on 1 aw Q.
0 a
h n o ._
o . _)
m

c 14 ftA0.8BBO.T3 799 1.2 -4 *


(2)
. 1 c*o 2 + co >co a + c*o 10 3 A = 1-12
10 3B = 1-8 880 5.6 -4
c 13 867 5.0 -4 ( x)
898 8.3 -4
c 14 900 2.6 -3 77 ( 2) CD
(*) 01
c 13 917 1.3 -3 01
Argon 0-0.008 850 5.6 -4 ( 2)
N2 0.0005 850 1.2 -3
0.0003 900 4.6 -3

COMMENTS
Reference. (*) Used mass-spec trome trie method with enriched C 13 or O 18 to follow exchange. Results of *) recalculated
by f 2) to fit empirical rate law of ( 2). Definite heterogeneous catalysis observed by (*) with quartz or gold surface,
also catalysis by HO or H 2 with concentration^. 000 2 increasing rate by a factor of five. ( 2) Increased S/V ratio

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
301.464

COMMENTS (continued}

by factor of 6 using packed quartz vessel with almost neglig


ible effect, but still concluded reaction to be predominantly
heterogeneous because of the erratic nature of results.
Both observed normal first order exchange rate (McKay rate
law)
and chemical kinetic rate law obtained from variation of
exchange rate with concentrations of reactants.

CO

(Si

Oi
Oi
LITERATURE
C 1) j. D. Brandner, H. G. Urey, J. C.P. 1945 13, 351.

( 8) T.H. Norris, & Ruben, J.C.P. 19SO, 18, 1595.

National Bureau of Standards- National Research


Council . December, 1955
2=
f z ffl
rf* 03 CO - P o
3
o
O O O 0
as a a H*
0*
*xj H-t 0
H* + +
~vj QD
i f_<
10
"*"
O
N" El
-50
X o
g * 0 o CD
M 0>
M O
"* 1 P o"
CO
CO 0
1 33
0 a CT ^
a
W

i i * e
0

* 8
4-
9
O
0 *~* 0 0
h-1 t-t 3
* HH +
df
+ a 0
h-1
o
(0
o
a S
CO
(f>
H* h* t tt
l-^ I"*

I I
O O
O O O O t ca
2r
10*8=
SO 104
A=l-8;
II H h* M-
II
Cft Cft 01 CO IT D 0
** -h l-s
si to -3
a -a o O
3 "0
CD CD
^3
^
Q.
a.

II n
<p, p, 10 3
Q rn
0. r: X
CO
"2-O
co co a
CO
CO CO O o
If If 8 e- c O
rn
^ CO
^ O ? i 0
3 w
o o - 0 ct Ct
O
o> O
1- H*
a
ar
V Def i ned mass-
s s
> > r^ act ion law
o
(0 O
ii 3
Cji ^ ,fx 4x O3COHk ^^^tf'-^WOJ
H^cocnro -acnco cftcnwroocD^ CO O ^ Temperature
oooo cnocn cnocnocnOcn S o o cn
OOCOCDM- i-^co^coh^^co ^ cn co
CDCftroCn ^^W CftCO^^H-^ODCO Cft en ->3 o o o CO ^
X
^ " o
i i i i iii i i i i i i i i i i i ct
cncncftCft (-^Oflrf^ 4^cncncncncftcft CO CO W W
3 S
^ V 03 a *
U CO ^ w 03
P 3
- cr H- O
^ ^
"TL "~J 9 C
v ^Jr P
_ H
CD CD 3 o o
o 3 3 P P CD P
-!-
3 H- -V4
O. p
- > * P
* * * * Comments - 2. - i
VO Li terature
^* -J? ^ 3
VJ1
6Q6T
Homogeneous Reaction Kinetics
301.471
1
!* c fe = ji = 0>
m * i. fe x I0 n A x ion w L.
(0 cfl 3
Amount of E +J 3
No. React I on Amount of reactant Addend cd c
T3 C i_ S CO
addend 1_
<D O o C
Q. i
E k n ^ n 5
4- O 9
O (0 \ _J
O

.5 CHF2C1 4- HC1* * CHF2C1* 4- HC1 10 3A=1.3-6i 10 3B= 1.3-6 pyrex g],ass S/V=4-1800 feA*B* 360 -6 (l)
2.8 *
cm" 1 -6
375 5.3
405 1.47 -5
420 2.5 -5
465 8.7 -5 30.2 9 4
_o _ - _q
.6 CF Cl 4- HC1* > CFC1* 4- HC1 A ~ 10 > B ~ 10 3 *FX 405 <2 -7 C 1)
3 3 *
510 7 -7
.7 ClgCBr 4- Br * > Cl CBr* 4- BrBr* 10 2A=1-4J 10 3B=3-17 feAB^ 146 -5 ( 3)
2.97 *
159 9.63 -5
172 3.03 -4 , 8.
183 7.26 -4 33.1 5.6 12
10 3A=4-20; 10*6=3-5 feAB^ 150 7.2 -5
0
170 3.1 -4
200 2.9 -3
220 9.5 -3 29
OHO
V2 ' o.ooooel
0.00016J
(see comments)
1
i
.8 ClgCBr 4- Br* > Cl gCBr* 4- Br 10 SA=1-4J 10 3 [Br2]=3-17 feAB 146-183 ( 3)
10.3 7.9 10 *
7 ( 8)
.9 C H Br + HBr* > c 2H 5Br* + HBr 10 3A=2-16; 10 6B=3-2000 s/v= 1 cm 2/ cm 3 feA 200 4.0 -7 * ( 6)
2 200 5.8 -6
air 150 mm. 200 7.0 -7
S/V = 1 cm 2 / cm 3 243 3.0 -6
254 1.3 -5 32
.10 C 2H BBr + DBr* > c2H BBr* + DBr 10 3A=8; 10 3B ^ 3 258 6 -6 *
(6)
10 3A=2; 10 3B=l-4 306 2 -4
.11 (CHJ.CC1* 4- snCl not stated feAB 25 2 -1 >3 *
( a)
33 4

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
301.471

COMMENTS

General. Exchange follows general first order rate law culated rate constants independent of surface to volume
(McKay). Chemical kinetic order of exchange reactions ratio, S/V=4-1800 cm"1 . (.6) Pseudo first order rate
determined from variation of exchange rate with concen constant for isotopic equilibration gives order of magni
trations of reactants ( 4). tude only. (.7) Reaction homogeneous as proved by
Reaction: (.1) Rate law calculated by editor from half increasing S/V ratio by factor of 12. Quartz and Pyrex
times and concentrations of reactants. Listed because of vessels gave identical results. Addition of 0 2, H 20, and
excellent agreement of sixteen out of seventeen separate C1 2 in amounts indicated had no effect. Both f 3) and () I
values at 400C. (.2) Reaction predominantly hetero consider reaction to involve rapid equilibrium B
followed by rate determining step (.8). (.8) Calculated
geneous as rate constant found to be linear with respect
to surface to volume ratio, S/V, from 3 to 14 cm" 1 with from (.7) and equilibrium constant for reaction forming
straight line going through origin. Activity of surface in bromine atoms. Addition of HBr at [HBr] *0.038 results
in parallel formation of Cl gCH to extent of about 20% cf A
creased with use but reproducibility obtained by baking
(.3) Reaction predominantly hetero at half time of exchange. (.9) (.10) Reaction hetero
and evacuating.
geneous even at highest temperature in pyrex bulb of 1 I. geneous as increase of S/V ratio by factor of 6 increased
capacity. Packed reaction vessel gave straight line plot rate of exchange 200 times. Coating surface withDri-
of log fe vs. T" 1 . Activation energy 17 kcals. for hetero f ilm had no effect. Coating walls with black decomposi
geneous reaction and >32 kcals. for homogeneous reac tion product decreased rate and gave reproducible results,
but did not change activation energy. (.10) Parallel
tion estimated from slope of log fe vs. T" 1 plot at highest
T in unpacked flask. (.4) Reaction predominantly het H-D exchange about four orders of ten slower. See 301.401.
erogeneous as rate constant found to be linear with res (.11) Reaction partially heterogeneous as glass packing
pect to surface to volume ratio, S/V, from 3 to 14 cm" 1 increased exchange rate several fold. Authors also ob
with straight line going through origin, Activity of surface served less than 1% exchange in 6 hrs. at 200 C for SnCl
increased with use, but reproducibility obtained by baking with CH 3C1, C 8H B(CH 3)CHC1, CH 3CCl g and CC1 4.*
and evacuating. (.5) Reaction homogeneous as cal

December, 1959
National Bureau of Standards- National Research Council
Homogeneous Reaction Kinetics
301.471

LITERATURE

( x) J.E. Boggs, L.O. Brockway, ACS 1955, 77, 3444. ( 2 ) D. Clark, H. 0. Pritchard, A. F. Trotman-Dickenson, CSL 1954,
2633. ( 3) N. Davldson, J.H. Sullivan, J.C.P. 1.949, 17, 176. ( 4) G.M. Harris, TFS 1951, 47, 716. ( 6) R. A.
Howald, J.E. Wlllard, ACS 1955, 77, 2046. ( 6) J.B. Perl, F. Daniels, ACS 1950, 72, 424. ( 7 ) D. R. Stranks, TFS
1955, 51, 524. ( Q ) J. Wlllard, A. Miller, JCP 1949, 17, 163.

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reactions ISOTOPIC EXCHANGE Gas phase
301.474 Halogen in IVth group halide Amounts are in M/I.
Rate constants are
i n M/I and sec.

ctf ctf
k x iOn 10n
Amount of E

No. React i on Aat


react ant

36 + HC1 10 2A=1-5J l0 2B=i-2 90 2.7 -2


S1C1 + HC1 36
2.5 1-6 100 6.1 -2
2.2 0.7 108 9 -2 1.1 -18

COMMENTS
Rate constant of exchange reaction calculated from half time of Isotoplc equilibration and concentration of A+L and
B+M. Order with respect to A found to be 1.9 - 0.1 and B 0.95 - .05. Authors found no effect upon rate of reaction by a
threefold change In s/V or by strong Illumination.

LITERATURE

R. H. Berber, J.C.P. 1957, 27, 653.

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reactions ISOTOPIC EXCHANGE Gas phase
301.565 Oxides of Nitrogen Amounts are in M/I.
Rate constants are
i n M/ I and sec.

Ito * <D k = ^ =
cd rt L. 03 L.
3 b x tn^ ,4 x ion 3
Amount of Amount of E -*-
C C
No. React i on 0 -a 5 a 0 as
-o i-
<D _2 E
reactant addend E o
** Q- 0
'C g E fe ^ O
C n n _j
Q
h

.1 NO + N 150 N 150 + NO A+B = 0.0018 -35 >:L 3 * ( 2)


2 2

.2 N 150 + N 0 > NO + N 15NO 10 3A= 1.5-2J 10 4B=7- 10 feB -9 1.9 -3 * (i)


225 2 5
2-3 15-20 0 5.2 -3
CO 0-.03 0 5.2 -3
2
1-2 30 NO 0.002 0 1.6 -2
3-4 30-50 0 10 1.4 -2 16 3 10

COMMENTS
Reaction: (.1) Rate law not verified value gives only lower limit. (.2) Change of surface
volume ratio has no effect on rate in absence of NO.

LITERATURE
t 1) A. R. Amell, F. Daniels, ACS 1952, 74, 6210. ( 2) E. Lelfer, JCP 1940, 8, 301.

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reactions ISOTOPIC EXCHANGE Gas Phase
301.701 Hydrogen-hydrogen halide Amounts are in M/1.
Rate constants are
1n M/I and sec.

No. Reaction

.1 D + HC1 HD + DC1 fcAB 492 2.0 -3

511 5.3 -3

533 1.34 -2

553 2.9 -2
570 9.4 -2 53 15

COMMENTS
Homogeneous reaction accompanied by small amount of heterogeneous reaction, correction Tor which has been made. Unit con
verted from M/cc and temperatures from K. Authors assume Arrhenius constant A to have T* dependence and consequently give
52.1 and A = 6.3 x 10 10^

LITERATURE

P. Cross, H. Stelner, JCP, 1936, 4, 165.

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reactions ISOTOPIC EXCHANGE Gas phase
301.770 Halogen-halogen halide Amounts are in M/I.
Rate constants are
i n M/I and sec.
Rates are in g ram
atoms/I. and sec.
R listed under mass action law indicates quantity listed is rate of isotope exchange see ( 3)-

i
CO 0) fe = A = O
CO 36 1_ 0} L.
3 fe x ion A x iOn +J 3
E -t-> +
Cti c cU
No. React i on Amount of reactant L. <0
E E V.
<D 0 D
C D.
E -M
E O
CD
k ^ O
4- O n n _J
V J H
Q

.1 C1F3 + Fg 18 10 4A=3-120; 10 3B=8-36 feA 194 1.57 -5 * t 1)


224 5.0 -5
257 4.2 -4 29 4 8
.2 BrFfl + F2 10 4A=5.1; 10 3B=6.32 R 193 8.5 -7 * C 1)
14.7 6.32 193 8.0 -7
29.6 6.32 193 6.7 -7
55.2 6.32 193 5.6 -7
55.1 16.4 193 1.15 -6
55.1 35.6 193 2.25 -6
4.0 4.62 224 3.0 -6
12.5 4.62 224 3.7 -6
44.9 4.62 224 2.25 -6
84.5 4.62 224 2.12 -6
44.8 15.5 224 7.2 -6
44.8 32.6 224 1.38 -5
5.0 3.98 256 1.20 -5
15.0 3.98 256 9.8 -6
35.0 3.98 256 9.0 -6
86 3.98 256 7.2 -6
34.9 32.1 256 7.3

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
301.770

k =

1Q
No. React!on Amount of reactant

18 10 3A=3-ll; 10 2B=1.4-3 -5
181 2.7
1.4-20 0.3-3 194 3.3 -4

4-17 0.4-2.5 3.5 -3 40


224 15

COMMENTS
CO

General: For general treatment of isotope exchange Authors list 10 4 ^et .x as 4 .5, 18 and 85 at 194, 224 and i
reactions see ( 3). In cases where the rate constant for 257C respectively with Ehet> = 24. Addition of H gF 2 had
the chemical process responsible for exchange has not no effect on exchange rate. Preliminary experiments by (^
been explicitly determined the quantity listed under k indicated reaction about 10 times faster in aluminum reac
will be the rate of isotope exchange, R, in gram atoms per tion vessel. (.2) Exchange considered to be princi CO
liter per second. This is indicated by listing ."R in the pally heterogeneous with rate law given by:
"Defined mass action law column "t R^et.xByA/d+xB+yA) 2
R = . m-n-frB where x and y represent adsorption coefficients of B and
(m-& + n-g) t A respectively at the nickel halide surface of the nickel
where m and n are the number of exchangeable atoms of reaction vessel, Authors list 10 4 ^et x=5.5, 37 and 125
the labeled species in A and B respectivel y. A represents at 193, 224 and 256C respectively with Eheti = 23. Pre
the sum of [A] 4- [L] and represents the sum of liminary studies by (*) showed no effect by NiF 2 . (.3)
[B] + [M] t X is the fractional extent of isotopic equili Exchange considered to consist of simultaneous homo
bration having taken place at time t. geneous and heterogeneous reaction at nickel halide sur
Reaction: (.1) Authors consider exchange is simultane face of nickel reactor. Values listed are for the assumed
ously taking place by a heterogeneous and a homogeneous homogeneous reaction. Rate of the heterogeneous reac
reaction and have separated the total rate of exchange tion is expressed by R^e^= ^et.xByA/(l-KxB^yA) 2 , where
into these two parts. Values listed are for the assumed x and y represent adsorption coefficients of B and A re
homogeneous reaction. Rate of the heterogeneous reaction, spectively at the reaction vessel surface. Authors list
is given by Rhet." *het. xByA/(l+xB+yA) 2 , where x and y 10\et< x as 4.5, 6.2 and 25 at 181, 194 and 224C.
represent adsorption coefficients of B and A respectively respectively with Enett = 18.5.
at the nickel halide surface of the nickel reaction vessel.

National Bureau of Standards - National Research CouncM December, 1959


Homogeneous Reaction Kinetics
301.770

LITERATURE

(*) R.M. Adams, R. B. Bernstein, J.J. Katz, J.C.P. 1954, 22, 13. ( 2) R.B. Bern
stein, J.J. Katz, J.P.C. 1952, 56, 885. ( 3) G.M. Harris, TFS 1951, 47, 716.

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reactions ISOTOPIC EXCHANGE Liquid phase
302.150 Ammonia(ammine) complex on Group lelement Amounts are in M/I.
Rate constants are
In M/I and sec.
Time of fractional
exchange In seconds.

fimaneds - u
k "ion L.
3 K
v
1.0 *
c ilaw
ction -M Comments
Amount of rt
Reaction Solvent L.
No. 0 Time to
X +j
reactant Q_
E
(D rt
0

.1 CU(N 18HJ^ + NH NH 3 10 3A = 6 100 180 -33 ^


34 3

10 2A = 2 -33 fZ \
.2 Ag (N 18H 3 ) 2+ + N3 NH 3 99.6 30

sH-4- >^ ^ ++ -3 f 1)
.3 Cu Ke + Cu > Cu Ke + Cu pyrldlne 10 3A = 10 3B = 1.5-15 feAB 25 2.6 *
2 2
(copper II sal I cy 1 a4 dehydeethy 1 ened! Imi ne)

COMMENTS

(.3) Rate law with respect to A and B individually not verified as A = B In all experiments.

LITERATURE

( l) R.B. Duf field, M. Calvin, ACS 1946, 68, 557. ( 2) H.U.D. Wlesendanger, W.H. Jones, C. S. Garner, JCP 1957, 27, 668.

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reactions !SOTO!C EXCHANGE Liquid phase
302.170 Halogen complex on group I element Amounts are In M/I.
Rate constants are
In M/1 and sec.

i o fe =
V) * A ^ x ion
3 fe x I0n
c Amount of Amount of -H
No. React i on > Addend rt
g
reactant addend o o (I)
CO
c
E
fe n ^ n
<D J h-
O

.1 AuCl ~ + 4C1*~ > AuCl *" + 4Cl" H 0 10 3 A = 3-12; HC1 0.003-.012") fe A + fe 0AB 0 fe 3.3 -3
4 4 2 1 2
10 B = 8-76 NaCl //,= 0.088 1 0 fe 1.83 -1
J 2
10 fe 4.5 -3 4 8 2
10 fe 5.4 -1 16 2 14
2
/X = 0.248 0 fe 2.5 -1
2

COMMENTS
(.1) Value of k calculated at u - 0.248 on basis of assumed no change for fe with Ionic strength.
2 ^ 1

LITERATURE
R.L. Rich, H. Taube, JPC 1954, 58, 1.

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reactions ISOTOPIC EXCHANGE Liquid phase
302.190 Valence states group I ion Amounts are In M/l.
Rate constants are
i n M/I and sec.

A =
A x 10

Amount of
No. Reaction Addend
reactant

Ag+a ~> Ag+ + Ag*+2 HC10 5.87 -15 3.0 +2


.1 10 (A+B)=5-16; A/B=5-17
3-31 2-25 5.87 0 1.02 +3
5-8 5-20 4.9 0 1.8 +3
10 20 4.4 0 3.1 +3
8 20-30 3.94 0 4.9 +3
4-18 &-20 5.87 11 2.74 +3 12.5 1.1 13

COMMENTS

In the limited range studied reaction appears to follow inverse fourth order with respect to H .
Mechanism of exchange probably involves a rapid equilibrium of the type 2Ag 2 <-_ Ag + Ag+3 .

LITERATURE

B.M. Gordon, A. C. Wahl, ACS 1958, 80, 873.

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reactions ISOTOPIC EXCHANGE Liquid phase
302.240 Cyanide complex group II element Amounts are in M/l.
Rate constants are
In M/I and sec.

k A
i
ned
fmas - fe x 10n
1
i
letawon Comments L
i
terature
So
1
vent Amount of Amount of
No. Reaction Addend *
reactant addend . fe n A n
0

.1 Zn(CN) 4 ~ 2 + C 14N~
H 20 A = B = 0.025 KOH PH - 10.3 25 very fast * 0
.2 HgCN+ + Hg**" ^ Hg*CN"*" + Hg* 10 3A-2-16; 10 3B=6-49
H 80 HN0 3 pH=2.4-2.8 feAB 0 7 -3 * ('M 8)
7 2 /I =0.12 9 1.6 -2
17 3.5 -2
25 6 -2
30 9 -2 14 1 9

.3 HgCN* + Hg*2* ~~"^ Hg*CN"*" + Hg2"*" 10 3A=6-34; 10 4B=6-200


H 2 NaC10 4 1 pH=1.5~2.8 -2 ( 3)
feAB 0 1.7 *
HC10 4 | ^6=0.02-. 12 13 4.9 -2
20 9.2 -2 13 6 8
fe*AB 0 1.3 -2
13 3.4 -2
20 6.0 -2 12 4 7
COMMENTS
Reaction: (.1) Complete exchange within 120 seconds. (.2) In absence of CN~ exchange Is Immeasurably fast. Rate
constant calculated by ( 2) from rate data of (*). No effect on rate observable by authors of pH=0.85-2.7, Ionic strength=
0.1-2., 0 2=0. i-760 mm of Hg. or colloidal Hg. (.3) Rate constant listed as fe Is observed value calculated frompseudo
first order exchange rate and concentrations of A and B. Rate constant listed as fe* Is value of constant corrected by au
thors for apparent exchange caused by the disproportionate reaction 2HgCN+ <- Hg+ "*~ + Hg(CN) .
2

L. __-

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.240

LITERATURE

(*) A.C. MacDlannld, N. F. Hall, ACS 1954, 76, 4222.


( 2) R.L. Wolfgang, R.W. Dodson, JPC 1952, 56, 872.
( 3) R.L. Wolfgang, R.W. Dodson, ACS 1954, 76, 2004.
CO
cn
co

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reactions ISOTOPIC EXCHANGE Liquid phase
302.390 Valence states Group III ions Amounts are in M/I.
Rate constants are
i n M/ I and sec.
Coded solvents at
end of tab I e.

Concentrations in gross concentration of all forms unless Indicated otherwise.

4> k = A =
L. o
-H 3 fe x ion A x ion 09 i_
-H +* 3
c Amount of Amount of Def i ned mass- Cti C -M
0) cd
No. React! on Addend U s C
reactant addend act 1 on 1 aw E i-
o Q_ E o
CO E 0
V fe<> n ,4 n 0
\- -J

Ce 3|H" 3 +Ce"1"4 > Ce^+Ce* 4"4 10 3A=2-18; 10 3B=2-17 -14 -2 (15)


.1 H 2 HNO g 6.00 feAB 1.28
-10 -2 (12)
/X = 6.18 1.00 6.9 *
2.01 -10 3.0 -2
1.00 - 6 1.16 -1
-1 (IS) (4)
1.00 0 3.2
-2 (12)
2.01 0 9.8
2.42 0 7.5 -2
3.68 0 4.2 -2
-2 ( 11, { 12, ( 15,
6.18 0 3.7
6.18 25 2.9 -1 12 1 8
THNO 6.00
-14 -1 (IB)
IKF 0.00013 1.11
0.00025 -14 2.3 -1
0.00047 -14 4.2 -1
0.00063 -14 5.0 -1
0.00080 -14 6.7 -1
0.00080 0 1.02 0
10 3A=l-9; 10 3B=1-10 -1 (8)(27)
H SO 0.4 feAB 0 4.2
-1 (27)
0.5 0.5 10 1.16
-2 (10)
0.8-8 1-10 HC10 4 6.0 feAB+fe'AB 2 0 fc 5
0 fe'9.3 0

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.390
0 k = A =
i_ A x ion 0
0 x 1Qn CO V.
-H 3 4-J
-H 3
C Amount of Amount of Def 1 ned mass- C +-
0>
cd
Addend u 0 tf
No. React i on >
actlon law v> # E U
' reactant addend a. E a>
-M
E
43 * n ^ n S
H _J

Ce**" 3 + Ce"4"4 > (continued) 10 3A=0.8-8J 10 3B=1-10 * (10)


.1 H,0 HC10 4 5.85 feAB+fe'AB 2 0 k 9.3
0 fe'9.8
5.04 0 k 1.5 -1
0 fe'1.44 +1
3.97 0 k 4.8 -1
3.00 0 k 7.0 -1
2.04 0 k 1.12 0
10 3A=2-20; 10 3B=2~42 -5 (18)
H 20 6.18 V+VB 0 kj *
4
0 k 6.7 -3
10 k 3 -4 19 3 11
10 V-9 -2 17 2 11

EU*+8+EU+3~>EU+8+EU*+3 10 2A=3-7; 10 2B=3-12 0.1-1.6 T fcABtcT] 32 8.2 -4 *


.2 H20 JO
-3 (20) (21) CJl
0.1-2 > 39 1.80
CO
50 5.3 -3 21 6 11
NaC104 fjL=2.0 J

10 2A=10 2B=2.44 -3 (23)


T1*+i+T1+3_^ T1+1+ T1*+3 2 HN0 0 1.0 kAB 25 1.6 *
.3 U
1.5 25 2.3 -3
10 4A=8-85; 10 4B=8-34 -3 ( 5)
H 2 S0 4 1*6 0 2,25
1.6 25 1.98 -2
-2 ( 3)
2.2 25 1.3
-2 ( B)
1.6 44 7.7 14 3 8
-2 ( 3)
10 2 A=10 2B=1.0 H 8 S0 4 =7j30; Na2 S0 4 -0.39 25 1.60
1.28 0.57 25 1.80 -2
/I=3.68
0.85 0.80 25 2.33 -2
0.65 0.95 25 2.92 -2
-5 (30)
10 2A=10 2B=1.0 H 2 S0 4 =0.0 HC10 4 = 3.12 24 6.4
0.006 3.11 24 1.0 -4
0.015 3.10 24 1.6 -4
0.030 3.09 24 2.6 -4

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.390
k - A
<D
k x 1 On A x 10 n
Amount of Comments tLi
erature
vent
1
So Amount of Defined mass-
No. React i on Addend i
reactant addend action taw
[ n A n

.3 T1 *+i + n+3 > (continued) H 20 10 2A=10 2B=1.0 HC10 4 =3.07 feAB 24 -4 ( 30)
H 2so4 = c).047; 3.5 *
c).093 3.03 24 7.4 -4
c).158 2.96 24 1.1 -3
0 3.12 37 1.8 -4
c .015 3.10 37 4.4 -4
c).030 3.09 37 7.0 -4
c).047 3.07 37 9.7 -4
c).093 3.03 37 1.7 -3
c).158 2.96 37 2.9 -3
c).49 2.63 37 1.05 P
H20 10 2A=10 2B=1.0 H 2 S0 4 = 0 ; NaC10 4= 3. 12 k AB 50 5.0 -4 15 1 7
n c).047 3.07 50 2.7 -3 15 4 7
n c).093 3.03 50 4.8 -3 14 1 7 JO
n -3 Oi
c).158 2.96 50 5.3 12 4 5 CO
10 2ACyl.O;10 2B=1.08 H 2 S04 =^1. 19; HC1= 0.0010 25 1.18 -2 ( 3)
ii n .0030 25 1.03 -2
n n .0050 25 6.8 -3
n if .0080 25 3.7 -3
n n .010 25 2.2 -3
1. 15 .014 25 8.2 -4
n n .017 25 2.3 -4
it n .02-. 03 25 g..fi -5
" '1.08 .04 25 6.7 -5
0.5 0.65 .025 25 6.8 -5
1.0 1.08 .049 25 9.8 -5
0.5 0.65 .030 25 1.07 -4
n n .035 25 1.55 -4
n n .062 25 5.7 -4

National Bureau of Standards - National Research Council December, 1959


o
+

CO
CD
P
CO
o
on !
React J3
4
O
o
So 1 vent
10
0
s
s 10
Al
i ro
of
reactant Amount
On
o S
to
II Al
1 ro
01
0
~ + K
p o OL
a.
o> o ^ 1 5 CD
CO 1^ 3
b o ii X
,*_,
T: o o >
2. PT
OOOOGqOOOOCflOOOOCfl *
Q- o
1A -h
O
1 p *
0 ^
ca *%
STVo^ **
5 i' i.
i
-T M
jororororororororotocnmcncjicji 888^S3ggSg5S5
FwF^tFJ*^ ****** ***?''
OIO^OOOD^WWWWCO^^^WC
03Oirf^H*-i^|-k'^l-*'^l-l>O5OD
O3 "-3 Ol *"* CD CO Ol tf^ tO 0 ?r
O M> Ol X
I 1 1 1 1 1 1 i 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 3 ^
mcndoioiuicnoicncncbcncncnoi
M- M> t N
OJ B 00
ro co i^ ^ "^
S3 "
CD ro oo
O * Comments
0
O
H* (0
L i teratu re
VO
VJ1
Homogeneous Reaction Kinetics
302. 390

A o
reatu
erTemp fe x 1.On A x 10n
c snt
Comme 3
0 Amount of Amount of Defined mass-
No. React i on Addend S L.
r eactan t addend ac ti on 1 aw C
o H
CO
k n A n

T1 * + 1 + T1+3 > (continued) 10 2A-3; 10 3B = 4 ( 9)


.3 HC104 = 0.5 feAB 50 2.06 -4 *
V
+ Naciol 1.0 50 1.83 -4
IJL= 6.0 J 2.0 50 1.58 -4
4.0 50 1.19 -4
6.0 50 1.05 -4
/z= 4.0 0.5 50 5.54 -4
1.0 50 4. 34 -4
2.0 50 4.06 -4
-4 ( 9 ) ( 13 )
4.0 50 3.92
-4 ( 9)
H= 2.0 0.5 50 6.7
-4 3
1.0 50 8.1 r*
2.0 50 8.1 -4
K4
/x= 1.0 0.5 50 7.4 -4 CO
Oi
-4 ( 9 ) ( 13 ) CO
1.0 50 8.7
/x= 0.5 0.5 50 7.4 -4
-5 ( 14 )
10 4A = 1- 250; 10 4B= 1- 17C HC10 4 6.0 feAB 32 1.93
0.01 32 <6 -9
0.02 32 1.7 -8
0.06 32 3 -6
0. 12 32 3.0 -5
0.20 32 9.7 -5
0.40 32 7.6 -4
1.00 32 6.4 -3
1.50 32 9.6 -3
0.40 42 3.6 -3
1.50 42 3.1 -2
10 3A=5-50;10 3B = 5~50 HC10 3.50
-5 ( 2)
+ CH COOH^ 0.005 25 3.6
0.010 25 3.5 -5
0.020 25 3.2 -5
0.050 25 2.6 -5

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.390

0) fe = X = 05
i_ 0) L.
-H 3 fe x 10n ^ x lQn 4- 3
C V C V
07 Amount of Amount of Defined mass- cd O rf
Reaction > Addend u 1? e 1_
No. 0 4>
reactant addend action law E -H
0 D- O
OD E fe X O
<D n n _J
H-

.3 T1*+i + T1+3 > (continued) H 2Q 10 3A=5-50;10 3B = 5-50_ HC10 4 ( 8)


_ 3.50 feAB *
+ (CH COOH) =0.003 25 3.4 -5
0.010 25 3.4 -5
0.020 25 3.1 -5
0.050 25 1.7 -5
HC10 4 0.5
-4 ( 22 )
+ HCN = 0 30 2.1
0.1 x B 30 1.7 -4
0.5 x B 30 1.0 -4
1.0 x B 30 4.6 -5
*7 V TJ -6
1 * / -^ D 30 3.0
V 15 -6
2 CO * D 30 2.2
K*
3 x B 30 1.0 -6 CO

NaCN 17 x B 30 5.8 -5
no v D 2.0 -4
j\J ^ D 30
34 x B 30 4.7 -4
44 x B 30 1.2 -3
68 x B 30 5.1 -3
85 x B 30 1.3 -2

u+4 + u*+a_> tfM-4 + ^e 3 -6 * (i)


.4 H 20 10 2A=2.0; 10 2B=2.0 H 2S04 1.91 feAB 30
10 2A=3-6J 10 2B=2.7 HCl.NaCl PH--0.85J feA 2B 25 5.0 -3 ( 19)( 85)
2.5 2-15 NaC10 4 25 3.2 -3
-2 (19)
Et30* 10 2A=l-3; 10 2B= 1.5-3 HC1 0.0326 feAB 25 2.1
2 2-4 0.0651 25 6.9 -3
'- -3
2 2 0.130 25 2.0
Et60* 2 3 0,0326 feAB 25 5.0 -2
2 3 0.0651 25 2.3 -2
1-3 2-4 0.130 25 1.33 -2

National Bureau of Standards - National Research Council December, 1959


o> 01 ^ 0 Io
g^ I
^ *
01
8
i 4
Jt +
+ 0>
on
ReaotI
i I
^
i
o
Of
5 T
3.
*.
^ 3
"*" CO
* 2: Si
0>
jU O M
10 So 1 vent
o o
" "* 8
o o
CO M
s
*y ^ (-^-M-i-^OH^Oh-*-
0
g 5 oi N g. >a o> ^a
fs ; s n> *-*
Q i. S
f tfl1 II ^
CO " J^
CO
g 8 ^|^g-F-
GO
CD oq pj O
** '-"^ o ' Q.
0 0 M 0 Q.
I-1 I-1 O 4t O 1' ^
O O i^ u S 3
0.
to
3>
>- >: ^ " i^ oooo o o o ~ 3
\t J 0
jj O 03 O I^L T*
*i 5it
03 0 O3 W !-*(-" OO M-^WOH'-OlOO
O ,_x CO CO W o> ^ ^ v__ C^0> o M. *3 fo en1 -i^ ii^1 OD M
- o
03 Y *" ^ 03
0
II 9
0 -h
ar \
to w ar jv
0 0
~ ^ w > 3 a.
5S ffi^ . w w
3
s P ^
3E 09
10 7
Ol Ol O O oooo oo oo ^^rfs.^rvj^ft) loforororowro Temperature
si -si ->a sj 01 ^i 01 oioioioioioioi
h-^^03 0003 03W 03fohj'COHi-oia> -^ro-J[ft)t->-t--ro *o ^
rooo>o> coi-- on1- OJ(--COD|--O(^ OftM'OC^^OOOl
01 ^ 0> X
+ + + + + + + + + + + + 1 1 1 1 1 1 1 + 3 Oj
M- I-*-
Ol JO 5 S! N
- -* O>
^ **
^ ^
X
f-*- f-* s"
00
* * * Comments
M Li terature
3 33 3 3
Homogeneous Reaction Kinetics
302.390

]
L. fe = A = <D
-M A x ion CO L.
3 fe x jnn
c H
Amount of Amount of Defined mass- -*-
No. Cti C
Reaction Addend u i V <b
reactant addend act! on 1 aw 0) E
o>
o CL E -H
CO E
1- k n A n S _J

.6 Np* 4" 5 4- Np4"6 > (continued) H 20 10 5A=3-10; 10 5B=2-9 HC10 4 } [H+]=0.3-l\


4-1 ( ?)
feAB 10 5.1 8 1 8 *
Nacioj M = 1.0 J
10 BA=10 5B=2 [H+] = 3 /JL- 3 (8)

Cl~ = 0.10 0 1.07 4-2

0.23 0 1.19 4-2


0.55 0 1.32 4-2
1.37 0 1.52 4-2
1.5-2.7 0 1.6 4-2

0.21 5 1.75 4-2

0.55 5 1.92 4-2


1.37 5 2.4 4-2
0.21 10 2.4 4-2
0.55 10 2.9 4-2
4-2 CO
1.37 10 4.0

DBO 10A= 10 B= 2 NaC10 4 ^.3il


DC10 4= 5 5.4 4-1
'feAB 4-1
1.0 r 5 6.6
3.0 J 5 9.8 4-1

PU* 4" 3 + PU+4 > PU4" 3 4- PU* 4" 4 10A.SS10B-8 * ( la)( 17)
.7 H aO HC10 4 0.4-2J fe-AB 4- 0 *t 4-2
L1C10 4 /^=2.0/ fe^IpuOH4" 3-! 0 fe2 1.3 4-4
4-2 ( l )
12 fe 4
12 fe2 1.2 4-4
25 fe l 2 4-1 8 3 8
25 4-4 3 2 6

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.390

CODED SOLVENTS
Et30* (60) (90) 2
c 2H o OH vol. % Indicated + H 00

COMMENTS

Reaction: (.1) Rate constants calculated on basis of change by platinum foil, and also studied x-ray induced
first order dependence with respect to each reactant al exchange. Selected data of t 3). Dependence of calculated CO
though log plot indicated order with respect to B to be second order constant upon [H 4"] not completely deter
0.9 * .05. Rate constants calculated from data of ( ltf) in mined. ( 14) ( 24) ( 20) express k=k o +k'[ti+] ~* based upon
half times. ( 12) observe that plot of rate constant vs. parallel exchange occurring with Tl* 3 and T1(OH) + 2 ions
[H 4"] "2 is linear. ( l9) observe that plot of rate versus as exchanging species with Tl* *. In contrast (*) uses
[KF] is linear. ( 10) concludes that data conforms to rate k- l=k'+k"[H+] based upon the assumption Tl(OH)"1" 2 is
lawR-iJCe"1-*] [Ce(OH) 8+ ] + A 2(Ce+ "KHOCeOCe* *). the only exchanging species. Plots of k vs. [H"4"]" 1 and CO
Values of k and h 8 are not given. In range B = 0.0009 also A"1 vs. [H 4" ] show some curvature for all data col cn
co
to 0.010 ( 10) finds plot of RA^B- 1 linear with respect to lected. Tables are therefore composed principally of the
B and concludes reaction is best expressed by the com of the second order rate constants based upon total con
bined second and third order rate law given. In range centrations of the reacting species, as determined by the
6=0.002-0.04 ( 12) finds plot of RA' 1 linear with respect various investigators, with concentrations of acids and
to B but straight line does not go through the origin. ( 12) added salts given. Selected data for reasons of conserva
therefore concludes reaction is best expressed by the com tion of space. Ions such as Cl~ and CN" both reduce ex
bined first and second order rate law given. (.2) Vari change rate at low concentration and increase rate at
ation of [H 4"] from 0.1 to 1.56 caused change in calcu higher concentrations. (.4) Exchange observed by (*)
lated k of only 1.60 x 1CT 3 to 1.82 x 10" 3 at 39C. to be about 20 times faster when illuminated by 300 watt
(.3) Data of ( 23) calculated for rate law determined by lamp 4cm. from reaction flask than in dark. Value listed
later investigators. C 8) observed slight catalysis of ex is for reaction in dark. Activation energy of light reaction

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics 10
302.390

COMMENTS (continued)

8 kcals. ( 25) observed no effect of light in presence of greater than 0.5 exchange reaction shows positive depen
HC1 and a negligible salt effect. Exchange rate propor dence upon ionic strength and some catalysis by platinum
tional to [H + ] ~3 in the pH range 0.85 to 1.6 in H 20 as foil, gold foil and pyrex helices. At both the higher and
solvent, in mixed ethanol-water solvent ( 10) observed lower acidities the exchange reaction is faster than the
wide variation of order with solvent composition. Log-log oxidation-reduction disproportionation reaction. (.6)
plots gave best fit for the order 0.93 for A, 1.11 for B and Reaction found to be essentially independent of dielec
-1.74 for HC1 in 30 vol. % C 2H 5OH; 0.87 for A, 1.08 for B tric constant of solvent in range from 68 to 88.3 using CO
and -0.97 for HC1 in 60 vol. % C 2H BOH; 2.89 for A, 0.10 ethylene glycol or sucrose with H gO. At constant ionic
for B and -1.06 for HC1 in 90 vol. % C 2H 5OH; and 0.0 for strength exchange appears independent of [H + ] up to
HN0 3 =2.0. This is possibly due to slight retarding effect CD
A, 2.70 for B and -1.26 for HC1 in pure C 2H 5OH. ( 19) pro
poses rate expression is A;'[UOH+ 3] 2 [UO OH 4"] and observed for nitrate ion ( 8) balancing slight positive H* si
calculate k ' from the expression: 2 effect ( 29). Below /z=3.0 exchange rate is observed to be
independent of positive ion Na*, Mg"1"*" or La* 4"*". At CD
jjL>3, ( 29) shows that effect of Na 4" > Mg 4" 4" > La + + 4\ Oi
co
( 8) study catalysis by Cl" at constant [H"1"] and ionic
.3.4x10-* strength. They suggest two reaction schemes:
V f
derived from the hydrolysis constants, 3.4*10~ 5 =
[UOH+ 3] [H+l/tlT 4] and 1.3xlQ- 5 = R =
[UO OH+] [H+]/[U0 2+ + ] No definite trends in the fe 2(NpO/)(Np0 2C! 2) and calculate the values of feo , k t
calculated fe' in any one solvent system although values and fe g according to each scheme. Data does not ap
vary by as much as a factor of two in both the 30 and the preciably differentiate between these two rate expressions.
60 vol.%ethanol. Agreement between values of calculated (.7) Slight positive dependence upon ionic strength in
fe f is better in the other solvents. (.5) At [H + ] less range 0.7 to 2. Values probably give little more than order
than 0.3 exchange reaction appears to be independent of of magnitude because of difficulties of measuring such a
ionic strength or glass or platinum surfaces. At [H"1"] rapid exchange.

December, 1959
National Bureau of Standards - National Research Council
Homogeneous Reaction Kinetics
302.390 11

LITERATURE
(*) R.H. Betts, CJR 1948, 26B, 702. ( 2) C. H. Brubaker, C. Andrade, ACS 1959, 81, 5282. ( 3) C.H. Brubaker,
K.D. Groves, J. P. Mickel, C.P. Knop, ACS 1957, 79, 4641. ( 4) G. E. Challenger, B.J. Masters, ACS 1955, 77, 1063.
( 5) G.E. Challenger, B.J. Masters, ACS 1956, 78, 3012. ( 6) D. Cohen, J. C. Sullivan, E. S. Amis, J. C. Hindman, ACS
1956, 78, 1543. ( 7 ) D. Cohen, J. C. Sullivan, J. C. Hlndman, ACS 1954, 76, 352. ( 8 ) D. Cohen, J. C. Sullivan, J. C.
Hlndman, ACS 1955, 77, 4964. ( 9 ) R.W. Dodson, ACS 1953, 75, 1795. ( 10 ) F. R. Duke, F. R. Parchen, ACS 1956, 78, 1540.

J.W. Gryder, R. W. Dodson, ACS 1949, 71, 1894. ( 12) J.W. Gryder, R. W. Dodson ACS 1951, 73, 2890.
( 13 )G. Harbottle, R.W. Dodson, ACS 1948, 70, 880. ( 14) G. Harbottle, R. W. Dodson, ACS 1951, 73, 2442. ( 1B) H. C.
Hornlg, W. F. Llbby, JPC 1952, 56, 869. ( 16 ) T. K. Keenan, JPC 1957, 61, 1117. ( 17 ) T.K. Keenan, ACS 1956, 78, 2339.
( 18) R.J. Marcus, B.J. .Zwollnskl, H. Eyrlng, JPC 1954, 58, 432. ( 19) D.M. Mathews, J. D. Hefley, E.S. Amis, JPC
1959, 63, 1236.

( 20 ) D.J. Meler, C. S. Garner, JPC 1952, 56, 853. ( 21) D.J. Meler, C. S. Garner, ACS 1951, 73, 1894. ( 22 ) E.
Penna-Franca, R. W. Dodson, ACS 1955, 77, 2650. ( 23) R.J. Prestwood, A. C. Wahl, ACS 1948, 70, 880. ( 24) R.J.
Prestwood, A.C. Wahl, ACS 1949, 71, 3137. ( 2B) E. Rona, ACS 1950, 72, 4339. ( 2e ) F.J.C. Rossottl, J. Inorg. &
Unclear Chem. 1955, 1, 159. ( 27 ) P.B. Slgler, B.J. Masters, ACS 1957, 79, 6353. ( 28 ) J.C. Sullivan, D. Cohen,
J.C. Hlndman, ACS 1954, 78, 4275. ( 89 ) J.C, Sullivan, D. Cohen, J.C, Hlndman, ACS 1957, 79, 3672. ( 30 ) D.R.
Wiles, CJC 1958, 36, 167.

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reactions ISOTOPE EXCHANGE Liquid phase
302.401 H-D,(T) exchange on aliphatic C Amounts are in M/I.
Rate constants are
i n gram atoms/1 and
sec.
Coded solvents at
end of table.
under rate law indicates rate constant is for measured pseudo first order rate of isotope equilibration.
en i
M- V) L. k = A = CD
V) * 0) U
M +1 ^ 0 -o ti cd 2 jo x -i^n -H 3
H
D Z
S Amount of H C E 01 C
ed
No. Reaction '-5 Addend C L.
3 " tJ C * E
reactant o "S tt 0 a. E
"o.^ C **
CO ^, E w E 'Jj
** k A
3" M- O K n n
CO Q

.11 (CH 3 ) g CHCH 8CH 8CH 3 + D^ A A sat. with B " FE 44 1.1 -5 *


()

.12 d-C 8H BCH(CH 3 )CH 8CH 8CH 3 + DgS0 4 A A sat. with B " FE 60 1.0 -5 *
( 10)

.13 "- C8H 18+ V4 A A sat. with B "E 60 2.7 -8 *


( 10)

.14 d-C 8H 5CH(CH 3)CH 2CH 8CH 2CH3 + C 2HBS0 3D A A sat. with B ". 104 4 -7 *
( 10)

.15 C 8H BCH(CH 3 )CH 8CH 8CH 2CH 3 + ClSOgD A A sat. with B *FE ~78 2 -6 ( 10)
-50 6 -6

.16 (CH 8 ),CCH 8CH,CH,CH > H-D 880 4 A A sat. with B feFE 60 5 9 *
( 10)

.17 d-C2HBCH(CH 3 )(CH2) 7 CH3 + D8 S0 4 A A sat. with B feFE 60 4 -6 < 10)


Unsaturated Hydrocarbons
.18 HC: CH + D 20 B B sat. with A phosphate PH=8.6 feA 25 2.6 -3 *
(*)
buffer 9.0 25 6.0 -3

.19 H C:CD + FLO B B sat. with A HC1 .01 feA 25 0 *


( l)
C 65 *
acetate buffer=.04 >H=5.0 25 2 -6
phosphate buffer=.02 7.0 25 7.1 -5
.02 7.9 25 5.1 -4

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.401
OJ i
c H- en * u
fe = A = 0)
O "0 05 *
-\r\n
v lu A x io n (0 L.
^o x
C E -H
Sol vent Amount of 0$ c
JU c ~o L. E <D R)
No. React! on Addend D -0 E L.
(Med i urn) reactan t ? 0)
0 S c: Qu E
E E O
Q_l-< '^ fe n A n O
-J
3
CO 0

.19 CLH.C:CD + H *00 (continued) B B sat. with A phosphate PH =


65 t 1)
buffer=.02 8.6 feA 25 1.3 -3 *
.05 8.6 25 1.5 -3
borate buffer=.014 9.0 25 4.6 -3
" .012 9.5 25 1.2 -2
7-9.5 feA[oH~] 25 4.6 +2

= B +3
(")
.20 H C : C" + H 00 <W A=0.4-1.4J (CH g) 4N+ feAB 25 3.4 *
2
C H C:CH + OH" > C 65
65
10 4B= 1-100
M=5

Ketones 1
-5 * (")
.21 .3 4- H *0 0 k+tt 2 vol. (A-f-L); K 2 C0 3 .001 feAB 35 3.1
A
GOCH 0 + DOH > CH 30 COCH 0D
CH 33
1 vol. (&fH) .003 35 7.8 -5 CO
cn
.01 35 9.0 -5 co
.03 35 1.09 -4
.01 40 1.47 -4 18 5 8

PU -5 * (")
.22 Ln POPU U 4-
LUun TI *^ PIT
^ uri nU ""^ UUv^n,.,. 4-
Lli pnpu JJUn
^ rinu B+L 2 vol. (AfL); K 2C0 3 .001 feAB 35 1.25
322 33
1 vol. (B+-M) .003 35 3.1 -5
.01 35 3.6 -5
.03 35 4.3 -5
.01 40 5.8 -5 19 7 8

-8 ( 81)
.23 di-C H C:OCD(C H JCH CH(CH.)_ +- HO 8.4D1* A=0.1;[CH 3 COOH] = [CH 3 COO-] 0.030 feA 98 5.7 *
DO DO2 o <&
0.050 98 9.8 -8
0.070 98 1.40 -7
0.100 98 2.05 -7

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.401
O3 k = A =
C I 0
**- -H L. jO v 4A^ V.
CO 9 fe x lQ n a * \J 0}
H . 0 C -0 d cd 3 D
c o -H
^ C E c
<D Z Solvent -H Amount of ffJ F Crf
<D i- El <D
No. E Reaction T3 C E
TJ <D 0
(Medi urn) o S T3 addend C Q.
E
0
Q- <y\ <c *" . -H E A O
O. r-4 M- O K n n _J
o id *~
CO o

-7 * ( 21 )
.24 di-C 6H BC:OCT(C 6H 5)CH 2CH(CH 3 ) 2 4- H 20 8.4D1* A=0.1; HC1 0.020 feA 98 5.2
/=0.1 0.040 98 1.05 -6
0.060 98 1.61 -6
GHgCOOH 0.50 98 3.9 -9
0.75 98 5.6 -9
1.00 98 7.8 -9
-8
J
CH o0 COONa 0.01 98 1.12
-8
0.02 98 2.01
0.06 98 6.1 -8
0.08 98 8.1 -8
0.10 98 1.03 -7
NaOH 0.0050 98 2.57 -5
0.0075 98 4.3 -5
CO
0.010 98 6.4 -5 cn
HC1 .02-. 06 feA[H+] 98 2.72 -5
CHgCOOH 0.5-1 feA[cH 3 COOH] 98 7.7 -9
CH 3 COON-a .01-0.1 feA[CH 3COO~] 98 1.05 -6
1 NaOH .005-. 01 feA [OH"] f~98 7.7 -3

Carboxyllc acid, (salt), (ester)

-7 ( 3)
.25 HCOONa + D gO B feF 160 3.3 *
183 1.42 -6
214 1.29 -5 30 4 8

-6 ( 3)
.26 DCOONa 4- H 20 B fe pE 179 1.91
195 7.1 -6
208 1.72 -5 34 3 10

^130 -7 * ( 2)
.27 .5 CH GOOD + DO > CH 2 DCOOD + DOH B feFfi 3
32 ( 4)
160 -2 -6

National Bureau of Standards - National Research Council December, 1959


z
S 8 8 3 o
8ig-S!88S2g8 S
Supplementing
1951 No. 0>
O
o on ^ ^ 0000--^--x-^ 0 8
a as o o acwwffioooo as ro
co w K tU ej co cj co tx! K 3: K co
0 "~ "- a s s s "o "o uo uo 8 s
W to ?o to MM. OtoOOOO O
10 O O O o>ooooooo i
ffi S3 W ffl ,.'0 ^^ 0 ' *-* *~* ^ O
CO W O O lo'O3:oto^^loto -f 3
O ffi 0 OOCH t3T)WOO
S aC to 0 otocroqp,o o
to to o o
O O O 10 8 o,ffi + + + + + +
o ac o tn to O O
O 10 O CB K+totoUOOO 1
o QH re Ol ffi O 10 tO 1C (0 I
ts X y. -f O <y O O O O Jy
** Sr' "4 o + M g ! *
- Mo - ** * o
O 1C CT
o <': M- o c.33 Q
10 0 01 0 o w o
ac N* o "o React
on
i
a: r g
O 0*
+
g CD
o 4-
N1.' " o
'JJ
0 G
co +
C? O
O
K
So I v e n t
rjd GO Cd CO tfltdtjdtdtntowtu td
(Medium)
|> j> j> >. >>^lr >>>>
*t *? *t '<? ? ? ? ? g g g ^ 1!
P r+
Oi rji 01 01 en o, s rrr^
^ o-h
dd
II
0 0 O O O O O I-*
to to J
to 10
Q.
ffi K K W M M* Ma T , g g z Q.
Ol Oi CS C
o o 0
o o "o -g "o Si w-f +"+%. D
ss a 25 a 25 23 Z ' '
(P p; pi p Q.
P P P
^ ; <^ <> O O O
Amount of
o c o o > ^ ^ >-
ro TJ '-: ro w w w ro ro addend
jtr ft- <xr ar r<o-?r?r'iO''ar r Def 1 ned mass-
^3 ^] **] ^3 rj|'Tj'T]Tirriaj'x] xj
W W M W WMMtdWWWW W act ton 1 aw
^
w ro rc w Temperatu re
01 en en 01 S 8 8 g g 8 8 8 S8S8
03 03 M- h*
S- CD f o> ? r ^^ *Z
*r
00 to W M" 00-3 r\3 0> M.
X
1 1 1 1 1 1 1 1 1 1 i 1
->3 ^i <i >a ->3 -Q OS 00 CJ1 O) O> O O>C3>OSOi . %"
f^l
*S
0 ^
X
s,"
* * * * ******** Commen ts
-4 *! -* <*|
L i terature
4-1-II0C0C&OOQD sj? *
6S6T
Ol o
S ?S 2 03 "^ C& Ol a ^ h
*
a '-^ O O O
o o" "o S S 8 o o o> w
10 10 10 CO CD O O 0) W W
WWW o o o w W Ol CM --" g
01 01 01 B9 "S Ol ^-x O O OJ CO
o o o f? C? 0 0 ^^ 0 W W
0 0 OJ WOO 10 W 10 N to
O O
pd
o>
8 "8 "8 W U O O O ea O ^-"
0 0 ^ P
W o O O
O O O o
o o o o w o o M- Ct
WWW a + + 0 0 W
O O M 0 0 W 0 0 0 W 10
W G o o ^^ ^D 10 O CM O
o o o o w <^ ,
0 0 a W -f O
~f~ o 01 w o
+ w MW W
0 W
o ro oi , + 0 + W Ol
ro w o
o 3J o
01 0 O N CO
0 G to W "o "a o
W a O Ol 10
Ol O 0 W
o o o oi
o
0 3
s
o
X
\
M
0
X
2! ^
33 J
10 00
J c
W a*
O O1
H-
0) So 1 vent
td td td td td td td bd dd tjj bd
O n- (Medi um)
C
0*
tf
f^ I** Jt* &* ?* CD "^
^
3
> > ?* o ?*?> It* !>
X (B | 1 j ) | 3 |p m
i,> i) ip <^ a c c c c 1 1 1 3 1 ) 1 1 O -j
Q
M M> 01 ro ro P **
ro ro w h* o *-* i\j ,_,. 01
01 01 0* = 0
0* 0
P
o o o 0 e^*
1 1 t H X
WWW
o o o 1' o o O O O 0 0 5*
o o o
0) Cft 0> w w
WWW o CL
ct- 01 01 P Ol Ol CM Ol <D
o o o o
o CD p 25 25
o o o 3L
o o o o
p p p a
CO
> J ? P Amount of
o o o o
888 to w addend
Defined mass-
-* 5 ? * * * * * * at
W M W M^ action law
-> M-
?o ro ro OJ *P>- O5 Ol O to O5 O5 000^ Temperature
Ol Ol Ol 8 00 000 Ol O O
to M- !- O5 03 TO iL 00 ff*. M- to ^ 01 to t-* Ol O3 ar
(-> O5 M- 01 c ro ^ oq f-o O5 M- I-J- 00 w to ^ M- *o 0^
X
H- "
1 i 1 ill iii 1 1 1 1 1 i 1 1
O> O5 Ol Ol Ol Ol ^ Ol Ol 3 3
s & *
^ to ^^
V
H- "
01 w 3 O
3
* * # Comments
* * * * * * * *
333 3 3- 3333 j? 3 3 """^ L i terature
Homogeneous Reaction Kinetics
302.401

M-
fe = ^ =
4- g O T3 fe x I0n 4 x 10 n V)
d *
C E
Amount of -*- O 0$ c
No. React! on -a Addend C T3 S c e)
reactant U 0 (D E
o
co o o cd
E E fe X
n n 8 _J
0

Tetra-alkyl ion of Vth group element

.54 (CH ) N4" + OD" D 80 A=0.3;B^O.S< -9 ( aa)


3 4 Na+,r = B,A feAB 84 3. 1 *
100 2.3 -8 33 6 11

.55 (CH ) P4" + OD~ D20 A=0.3; Na+,r = B,A feAB 27 9.8 -6 * ( a8)
o
8=0.26-0.4 56 4.7 -4 26 1 14
CO

.56 (CH ) As4" + OD" D 0 A-0 3-B^O '5 Na+, I" = B,A kFE 62 7.2 -6 * ( aa)
3 4

[
.57 (CH ) Sb4" + OD" D :P = B,A kFE 62 7 -7 * ( aa)
3 4

Tri-alkyl ion of Vlth group element


CO
.58 (CH ) S4" + OD" D20 A = 0.3; B^0.3 Na , I = B,A feAB 0 2.9 -6 * ( aa) Oi
CO
27 1.16 -4 22 2 12
r
.59 (CH 3 ) gSe4" + OD" D S0 A =0.3; B-^0' 3 Na , I = B,A feFE 62 1.3 -5 * ( aa)
.60 (CH J Te4" + OD"
C
A 0.1. 5>B""" ^).3 Na , I" -6 * ( 8a)
3 3 D30 = B,A feFE 62 4

.61 CH - CH 2 - S4" + OD~ H D p|


rZ^
,M- *'. -7 ( aa)
D 2 1, D U.ol = B, A 56 3 *

(b i eye 1 o [ 2. 2. l] heptane- 1-su 1 f on i um ion)

Alkyl sulfinyl, (sulfonyl)


.62 (^-C4H9 ) 2 SO + OD D 20 A-1; B =.2 Na4", i"
= B,A feF E 56 1.0 -8 * ( aa)

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.401
fe = ' A =
0) 0
_ fe x ion A x 1071 to u.
3 Jf> 3
-
Amount of Defined mass- c J
Amount of cd <D
si \- # L_
No. React i on > -o Addend E 4>
react ant addend act ion 1 aw o> E
~~ <i> Q.
-*-
0
w ^ E ji 0
0 fe n n _
H-

10 2A~5;B^0.4 ~~ D *
(8)
.63 'CH CH CH CH CDSO C H CH - + OH ~D150* feAB 50 1.67
2222 2643
60 5.2 -5
71 1.67 -4 24.4 5 11

-6 ("")
.64 CH 2 (CH 2 ) 4CDS0 2CeH 4CH g- + OH" D150* 10 2A~5;B^0.4 feAB 40 2.18 *

50 1.11 -5
70 8.4 -5
79 2.2 -4 25 1 12

Alkyl halldes
Na+ -4 (13)
10 2A=3; 10 2B=3 =B feAB 0 1.57 *
.65 CHC1 2 F + OH" > CC1 2 F~ + H 2 H 20
20 3.9 -3 25 2 16
CO
Na+ -5 (") Ox
10 2A=3*, 10 2&=3 =B feAB 0 8.9 * CO
.66 CDC1 2 F + OH" > CC1 2 F~ + DOH H 20
20 2.55 -3 26 1 17

Na^ -3 (")
10 8A~l; 10 2B=1.7 =B feAB 0 2.10 *
.67 CDBrCIF + OH" H 2
15 2.27 -2 25 1 17

10 2A^2 -2 ( 18 )
.68 CDBr 2 F + OH" |CH 3NH 2 0.041 feAB--fe 1 A[cH 3NH 2] 0 k 2.07 *
H 20
0.05/ 0 fe f 1.3 -5
ICH3NH 3C10 4
25 fe 7.3 -1 23 5 16

10 3A^3 -2 ( 16)
.69 CDI 2 F + OH" H 20 (CH 3NH 2 0.1121 feAB+fe / AtGH 3NH 2] 0 fe 5.07 *

LCH 3NH 3C10 4 0.096J 0 fe'2.7 -5


_ 4
20 fe 8.2 22 2 16
20 fe'6.7 -4 26 2 16

Na+ -1 (18)
10 2A=1.3; 10 DB=3.1 =B feAB 20 2.07 *
.70 CHCl g + OD~ D20

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.401

o k = A - 0
L- L.
3 X x ion CO
- ^ fe x I0n H 3
4J +*
Amount of Amount of Def I ned mass- Si c d
L. 0
No. React! on >
5 .f-o Addend S k.
~~ reactant addend action law
& *, Q. *->
E feo ^
0> n n _i
t

Na+ =B feAB 0 4.7 -3 * (16)


.71 CDClg + OH" H 80 10 2A=1.3J 10 3B=3. 1
41 0 5.0 -3
3.1 NaG104 .038 0 4.6 -3
3.1 20 1.02 -1
3.1 35 7.4 -1 24 8 16
.016 \ fcAB+fe'A[CH 3NH 2] 35 fe'3 -4
buffer .0012J
fe'ci

-1 (")
.72 CDBr 2Cl + OH" H,0 10 8A~15 buffer f .1-.2 \ feAB4-fe'A[NH 3] 0 * 1.44 *
NH 4C10 4 .15-.4J 0 fe'8 -7
35 k 1.38 +1 22 4 16
35 fe'1.9 -4
O
-2 (**)
.73 CDIC1 2 + OH" H 80 10 2A~l; buffer f NH 3 feAB+fe'A[NH g] 0 k 2.75 *
NH 4C10 4 :^.t} 0 fe'4 -7
35 k 3.14 0 23 3 16
35 fe'6.5 -5

^ -1 ( 14)
.74 CDBr o + OH" H20 10 2A~l; buffer f NH 3 feAB+fe'A[NH 3] 0 k 5.8 *
3
NH 4 C10 4 .15-.4J 0 fe'1.3 -5
20 fe 8.3 0
20 fe'2.0 -4
35 fe 4.7 4-1 20.8 3 16
35 fe'1.4 -3

.75 CDIg + OH" H 80 10 5A^5; buffer f NH 3 .02-. 05 feAB 0 6.0 -1 *


NH 4C10 4 .02-. 05 24 1.39 21 3 16

National Bureau of Standards - National Research Council December, 1959


00 00 CD 00 00 00 00 00 00 O
OD -^OiOl^GJtoH^O s 00 -3 O> o
09
7i> xvO p O O tt d-O ct-
r^ O N tUOOtap
gP ffi 0 o 01 W 3 13
W ^ 0 to n S gO
cD
i?-*-
-BrCH:CHBr 20
cD
i^+
-ClCH:CHCl
QQH
cis-BCE
rC+
D:CDBr gO
trD
an+
s-ClCH:CHCl
ao "xBq-'SgS
aT oaSSw^^gg
fon
React
M og + w S + |
ffi 2 1 1 O O + O i-j
0 0 0
10
o
o rt jj, So 1 vent
ts ^10A9 tH Cd CO OT tH da td do bd
(Wedi um)
CO
>-* > te
O Jl co CD co co co CO CO CO
ll P P P3
0
to 3 3
00 P*D Ct>fOa>CDCD T CD CD O)
i-a.rtctp.p.p.p.O. P p, p,
"^^Ttototototo k to
It
dOdfl |a'a ic> ic3 lo d
i<> i^ ts* tr $3*
tr pr ti4 {31 !^
OCOQNPPPPP P P P
Ol CO CD CO CO CO CO CO CO
1 CD (D CD CD CD CD CD CD
CO CD CO CO CO co CO CO
-*
O 0 0
B g w a Q.
a US MS MS BS 0S CO CJ CO CO Q.
0>
-o "+ ** " "| "s "| "| P iP SP SP Q.
o 8 S. 2
. H H ^ Y T T T 1 i I |
-^ ddddtototototo to to to
b
00
-h
O
ar
0 -+,
i> 3
o o
3 Q.
gi dOWMWMMWW CO f * -
O 3
I P (D
$ 0}
p t at
1
f? ^ ?
j^ ocoaoi-^tooitoto w to to Temperature
1^ fv>ft>00l0l010l M' C3> 01 w o
(D CD
^ l-^Wt:>'l-'M-^AM- M- Ol *$
-* 01 to <o -% to pa O O3 00 ^3 H> 0
p P
CO CO
rt rt
1 1 1 1 1 1 II 1 1 1 1
-
co oqaoco-Qoi -^Jco to f>l Cfc
N
X
3 O
3
* ******** H- * * * Comments
h* h* Li terature
*^ O^l^CDCDCOQCD CD CD
3 5
6961
Homogeneous Reaction Kinetics
302.401 10

CODED SOLVENTS
8.4D1 8.4 M dloxane in H20
Dl 50* 50 vol. dloxane with 50 vol. of H o

COMMENTS

General: For general treatment of isotope exchange reac (.20) Rate constant for exchange calculated from nuclear
tions see ( 12). In all cases where defined mass action law magnetic resonance measurements. Effective relaxation
is given as hF E the pseudo first order isotopic equilibra time is dependent upon rate constant of exchange reaction.
tion constant is given as the rate constant. This is cal (.21)(,22) Approximate values of rate constants for for
culated from the fractional exchange, X, at time, t, by us ward and reverse reaction of first step in isotope exchange
ing the equation k - l/'t in(l-x).In cases where the reverse calculated from analysis of rate of exchange and equili
exchange is negligible due to a large excess of one iso brium isotope distribution. Rate law with respect to A and
topic species this might be equal to first order rate con B not verified as ratio of (A+L) to (B+M) kept constant.
stant for the reaction but this is not verified unless ex (.23) Pseudo first order exchange rate law not verified
change dependence on reactant concentration has been de as concentration of A kept constant. Under same condi
termined. tions rate is about one fifth of observed rate of racemiza- Oi
Reaction: (.11) Exchange rate constant calculated from tion for H-substituted compound interpreted to indicate CO
only one fractional exchange time. (.12) Exchange an H/D isotope effect about equal to 5. (.24) Pseudo
rate constant an average of three fractional exchange times. first order rate law with respect to A not confirmed as con
(.13) Exchange rate constant calculated from only one centration of A kept constant. Ratio of catalytic constants
fractional exchange time. (.14) Average of exchange to the catalytic constants for racemization of H-substi-
rates at 102 and 104C. (.16) Exchange rate constant tuted compound averages about 11 interpreted to indicate
calculated from only one fractional exchange time. an H/T isotope effect about 11 compared to H/D effect of
(.18) Exchange rate corrected for amount of A in gas phase 5, see (.23). (.25) Partial conversion of salt to HCOOD
by multiplying observed exchange rate by ratio of total A had no effect on exchange rate. Excess DC1 however ac
to A in liquid phase. Exchange rate independent of rate of celerated exchange. (.27) Calculated from a half time
shaking under conditions used. Total buffer cone. = .02. of about 100 hrs. (.28)(.29)(.30)(.31)(.32) Calculated
(.19) Exchange rate corrected for amount of A in second from time for half exchange in hours. (.33) Calcu
liquid phase by multiplying observed exchange rate by lated from percent exchange per day. (.34) through
ratio of total A to amount of A in aqueous phase. Ex (.48) Approximate value of pseudo first order ex
change rate not dependent upon rate of shaking under change rate constant calculated from percent exchange
conditions used. at one time only. Exchange probably occurs only

National Bureau of Standards - National Research Council


December, 1959
Homogeneous Reaction Kinetics
302.401 11

COMMENTS ( continued)

at a-hydrogen. (.51)(.52)(.53) Approximate values as than exchange. Second order rate constant calculated by
pseudo first order exchange rate constant calculated from dividing pseudo first order exchange rate constant by
percent exchange at one time only. Exchange probably oc concentration of B. Rate law with respect to A not veri
curs only at a-hydrogen. (.54)(.55) Second order rate fied. (.76) Complete in 20 hours. Authors estimate
law not verified. Rate constant calculated by dividing rate under similar conditions about that of (.78). (.77)
pseudo first order exchange rate constant by concentration (.78) Approximate value of exchange rate constant based
of B. (.56)(.57) Approximate value as pseudo first on assumed identical extinction coefficients for C-D and
order exchange rate constant calculated from percent ex C-H. (.79) Second order rate constant calculated by
change at one time only. (.58) Rate law not verified dividing pseudo first order eguilibration constant by con
Second order rate constant calculated by dividing pseudo centration of [CH 3ONa] . Approximate values as extinc
first order exchange rate constant by concentration of B. tion coefficients for C-D and C-H assumed identical. Ex
(.59)(.60)(.61)(.62) Approximate value as pseudo first or change rate falls off rapidly probably due to parallel
der exchange rate constant calculated from percent ex elimination reaction. (.80)(.8l) Approximate value of i
change at one time only. (.63)(.64) Second order rate exchange rate constant based on assumed identical ex
constant calculated by dividing pseudo first order exchange tinction coefficients for C-D and C-H. (.82) Com
JO
rate constant by concentration of B. Activation energy plete in 20 hours. Authors estimate rate under similar con Ol
CO
recalculated and corrected by reviewer. (.65)(.66) ditions to be less than (.80). (.83)(.84) Approximate
Rate constant listed is for first step in isotope exchange value of exchange rate constant based on assumed identi
and hydrolysis reaction. Hydrolysis reaction yields as cal extinction coefficients for C-D and C-H. (.85)
products, NaF, Nad, HCOONa and CO. Constants are (.86) Simultaneous solvolysis reaction caused concen
based upon an assumed mechanism and steady state ap tration of Bto drop to half its initial value during exchange.
proximation. (.67) Concurrent hydrolysis reaction al Value of pseudo first order exchange rate constant cal
so studied, see 212All. Products of hydrolysis are NaBr, culated from time of half exchange in hours and should be
NaCl, NaF, HCOONa and CO. (.68) Simultaneous hy interpreted as only giving a rough order of magnitude.
drolysis reaction causes change of OH" concentration (.87) Second order rate constant identical within experi
during exchange. Samples titrated prior to determining D mental order to second order rate constant for exchange
content. For hydrolysis reaction see 212.471 listed by of radioactive chlorine isotope between A and B. (.88)
authors. (.69) Simultaneous hydrolysis reaction not as Simultaneous elimination reaction about 150 times faster
appreciable as in (.68) see 212All. (.70)(.71)(.72) than isotope exchange see 422.471. Exchange constant
(,73)(.74)(.75) Simultaneous solvolysis reaction is slower listed for order of magnitude only.

National Bureau of Standards - National Research Counci December, 1959


Homogeneous Reaction Kinetics
302.401
12

LITERATURE
(*) P. Balllnger, F. A. Long, ACS 1959, 81, 3148. ( 2) J. Bell, T. Hill, K.A. MacDonald, K,I. Reed, A. MacDonald,
CSL 1953, 3456. ( 3) L. D. C. Bok, M. D. Cohen, J.S. African Chem. lust. (X.S,) 1951, 4, 37. ( 4 ) L. D. C. Bok,
Z. Geib, Phys. Chen, 1939, A183, 353. ( 5) L. D. C. Bok, L. G. Mltchell, J.S. African Chem. Inst. (S.S.) 1951, 4, 51.
( 6 ) L. D. C. Bok, L.B. Fetters, CSL 1952, 1524. ( 7 ) W. G. Brown, K. Eberley, ACS 1940, 63, 113. ( 8 ) H. B. Charman,
G.U. D. Tiers, M.M. Kreevoy, G. Fllipovlch, ACS 1959, 81, 3149. ( 9 ) S.J. Cristol, D. D. Fix, ACS 1953, 75, 2647.
( 10 ) G. S. Gordon, R.L. Burwell, ACS 1949, 71, 2355.

( ll) J.O. Hal ford, L. G. Anderson, J. R. Bates, R. D. Swisher, ACS 1935, 57, 1663. ( 12) G.M. Harris, F.F.S. 1951,
47, 716. ( 13 ) J. Hine, N. W. Burske, ACS 1956, 78, 3337. ( 14) J. Hine, N. W. Burske, M. Hlne, P. B. Langford,
ACS 1957, 79, 1406. ( 15) J. Hine, R. Butterworth, P. B. Langford, ACS 1958, 80, 819. ( 16 ) J. Hine, R. C. Peek,
B. D. Oakes, ACS 1954, 76, 827. CO
( 17 ) T.J. Houser, R. B. Bernstein, R. G. Miekka, J. C. Angus, ACS 1955, 77, 6201. en
co
( 18 ) G.P. Miklukhin, DA9 1950, 70, 439. ( 19 ) S.I. Miller, W. G. Lee, ACS 1959, 81, 6313. ( 20 ) T. P. Nevell,
E. De Sales, C. L. Wilson, CSL 1939, 1188.

( 21 ) C. G. Swain, E. C. Stivers, J. F. Reuwer, Jr., L.J. Schaad, ACS 1958, 80, 5885. ( 22) W. von E. Doerlng,
A. K. Hoffmann, ACS 1955, 77, 521. ( 23 ) J. Weinstock, J.L. Bernardl, R. G. Pearson, ACS 1958, 80, 4961.

National Bureau of Standards - National Research Council


December, 1959
Homogeneous Reactions ISOTOPE EXCHANGE Liquid phase
302.402 H-D(T) exchange on aromatic C
Amounts are In M/l un | 8s
otherwise Indicated.
Rate constants are f n M/l
and sec.
The position of the substitution is Indicated in parentheses after the arrow in those cases where it has been determined.
&FA under rate law indicates rate constant is for measured first order rate of isotope equilibration.

k A ss
Demafinsed- 10n x 10n
actlawion Temperature terature
Li
Amount of Amount of Comments
i
No. React! on Sol vent Addend S
reactant ad de n d
n A n

-6 (19,
.4 C 6H 6D + H+ > H 20-HC10 4 B^ 10.43 cio4~ 10.43 * FA 25 2.82 *
11.01 11.01 25 1.75 -5
11.71 11.71 25 1.35 -4
H 2" H 2 S0 4 10 3A=8; wt % H g S0 4
66.5 ftFA -7 (*)
25 2.68 *
68.7 25 5.75 -7
73.5 25 3.52 -6
75.8 25 1.15 -5
79.2 25 4.53 -5
83.2 25 3,45 -4

C 6H BT + H+ > ~~ 5 (*)( 17 )
.4.1 H 20-H 2 S0 4 A=sat. ; wt % H 2 S0 4 = 79 > 25 2.9 *
1L
K+ =B feA -58 -i -7 * ( 7)
.5 CQH5 D + NH 2- > NH3 A=0.25-0.6;B=0.6

C H + ND "" > -4 (83)


.5.1 NDg B=0.06 feFA 25 2 *
66 2
0.03 25 1.7 -4

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.402

c 4>
at
* s * l_ k = X = OB L.
3 k x 10** 3
E X x ion +j
Amount of Amount of td C
No. React I on So 1 vent O C0
Addend ~
<D S
0 L. L.
O g E
reactant C *~" E 0
addend Q.
O
->
E fe ^ O
Cc 2 O n n _J

0


.6 o-CH 3C 6H 4D + H- > H 0-H SO A=sat. ; wt. % H 2 S0 4 = 6* * FA 25 3.56 -7 ( 6)
2 24 *
81.8 25 3.4 -4 (17) (18)

H 0f, 0-CF0O COOH Mole & A=24.6; CF 3 COOH= 62.9; H 20=12.5 * FA 70 6.0 7 (18)

.6.1 H 20-H 2 S0 4 A=sat. ; wt. % H gSO 4 = 81.8 fe ,A 25 1.8 -4 (18)


364 *
.7 o-CH C H D + H* > K+ = B ^33
364 NH 3 A=0.25-0.6; B=0.6 (no F easu rable <sxcharige InL 10 h rs.) ( 7)

.8 m-CH 3 C 6H 4D + H+ H 20-H 2 S0 4 10 3A = 2;wt. *H 2 S0 4 =66.0 feF A 25 8.2 -7 * ( e)


A=sat. 81.8 25 1.0 -5 (17) (18)

.8-1 H 20-H 2 S0 4 A=sat.;wt. #H 2 S0 4 =81.8 * FA 25 6.0 -6 (18)


*
EZ
.9 *>-CH 3C 6H 4D + H+ H 20-H 2 S0 4 10 3A=2;wt. % H 2 S0 4 =53.0 feFA 25 1.36 -7 * (")
58.5 25 9.4 -7
63.9 25 5.7 -6
68.9 25 5.0 -5
73.4 25 4.2 -4
H 20-CF 3 GOOH Mole % A=24.2;CF 3 COOH = 62.0; H 20=13.8 70 1.00 -6 (16)

1.8 81.9 16.3 70 7.7 -6 (18)

.9.1 -CH 3C 6H 4T + H+ H 20-H 2 S0 4 A = sat. ; wt. % H r$Q 4 = 81.8 , FA 25 1.7 -4 (18)


*

.10 C 6H 0CH g + T+ (o:^=47: l: 41) A 10 2B = 7 N0 2 .001-. 002 feB[NoJ 25 7 -4 ( l )(")


*
2-7 -2
.000 2-. 02 140 1.9 10 4 3
2-14 Snd 4 .007-0.5 feB[snClJ 25 2.2 -4
7 0.07 140 4.4 -3 10 5 3

.11 *>-(%,) 3CC6H4D + H+ H 20-CF 3 COOH Mole % A=1.8; CF 3COOH=81.9;H 20=16.3 feF A 70 8.2 -6 (16)
*

National Bureau of Standards - National Research Council December, 1957


Homogeneous Reaction Kinetics
302.402
k A
jfimaneds - h *< 10^ A >c 10n terature
Li
of
Amount actlawion "emperature Comments
Amount of addend
No. React! on So 1 vent Addend S
reac tant
k n A n
i
0

Phenols, phenolates and alkyl-phenyl ethers


ci- =B -7 * ( 8)
.12 C H OH + D4" H2 0 10 2A=2; 10 3B=42 feAB 90 1.33
6 5 -8
7.8 100 5.0
23.5 100 2.00 -7
42 100 3.8 -7
83 100 9.0 -7
118 100 1.4 -6
167 100 2.3 -6
222 100 3.5 -6 I
7.8 110 1.5 -7
42 110 1.11 -6
7.8 120 3.67 -7 27.2 5 8
42 120 2.56 -6 27.4 4 9
Oi
CO
C H O" + D4" OH~ ( 9)
.13 H 2 kAB 24.8 8 9
6 5

. 14 2, 6-D -4-CH C H OH + E+ H 20-H 2 S04 10 2A=2. 5; wt. % H SO =9.8 *> 25 6.1 -8 *


( 3) ( B)
Z 362 -7
14.5 25 1.73
19.3 25 4.00 -7
27.0 25 1.33 -6
34.5 25 4.70 -6
- 45.3 25 4.38 -5
25 3.95 -7
H 20-HC1 10 2A=2.5;wt. % HC1= 7.10
11.66 25 1.33 -6
15.16 25 3.89 -6
21.5 25 3.06 -5

-6 (19)
.15 0-CH 0 OC H D + H4" H 2~ H 2 S 4 10 3A=3.5; 5.18 feF A 25 1.49 *
o o 4 w -6
5.90 25 3.63
6.82 25 1.21 -5

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.402

k '-"ion A <D
Demafisned w k.
of Teremperatu k x A x 10n +> 3
Amount of
Amount d
adden law
action c
No. React i on <c (d
i_-
Sol vent Addend S E
reactant E e
0 +j
k n AQ n o _i

.15 * (")
o-CH o0 OC 6 H^D + H"1" (continued) H 20-H 2 S0 4 10 3A=3.5; K 2 S0 4 7.34 ^A 25 2.91 ~5
*
7.88 2F 5,2 ~5
CH COOH A^O.l K 2S0 4 0.550 25 1.40 -6
3
1.23 25 5.10 -6
2.64 25 4.50 -5
A^3 SO ^0.3 80 2.9 -5 ( l4)
_
H 04.
(mole ratio CH COOH: A: H SO =5:1:0.1) ^0.3 100 1.5 -4 22 1 9
324

.16 rn-CH OC H D + H+ H20-HC10 4 10 2A^1.5 HC10 -7 (19,


364 10.04 k\ 25 3.00 *
10.43 25 7.20 -7
11.01 25 3.24 -6
11.71 25 2.00 -5

10 3A=3.5 CO
.17 p-CROC H D + H* H 2~ H 2 S 4 H 2S4 3.51 k\ 25 2.93 -7 * (19)
3 64
4.86 25 1.85 -6
5.95 25 8.8 -6
6.77 25 2.55 -5
-
7.59 25 8.4 -5
CH COOH A^O.l H 2 SD 4 0.232 25 5.0 -7
0.632 25 3.00 -6
0.916 25 5.0 -6
1.72 25 2.30 -5
2.68 25 8.2 -5
3.52 25 2.10 -4
CH COOH A^3 H SO ^0.3 kF -5 ( 14)
3 -~- 24 A
80 8.8 *
(mole ratio CH 3 COOH:A:H SO =5:1:0.1) ^0.3 100 3.0 -4 16 7 5
- 24 _
10*A*8 ZnCl 1.90 _ry (20,
2
25 3.10
2.07 25 4.05 -7
2.68 25 8.2 -7
3.19 25 1.66 -6

National Bureau of Standards - National Research Council December, 1957


z
M- H- M- o
8 CD 00 <J o
OQ
T 1 <? T
9
CO
S
CO CO
8 3
C3
o o o o g
o o o o
"o *o *o *o
on
i
React
2; 2; 2; ffi
to to to ,^
' ' ' 8
c*.
Cu
0 CO
tc o
w w "o
CO CO CO g
u
H-
^
0
v
O
r
0
5
J?
$ (J
5
^
0 0 0 ^ ^ K^
| I
td Cp tud ii II ||
r+ _+,
S & & o A P
* o
o> 01 as j^ ^ en
01
Q.
3 g g Q.
0)
w+ w+ "V 2 p 0 f3 3
N t3 tO M Q.
M-OOO \5OOOOOM-N-OOOOO OOOOOO
Amount of
addend
jo ~vt en co oi OD co o o tf^> oo rf^ o o o H* o 01
?y* ^* ^ ^*
Temperature
Defined mass-
03 01 03 oi^CJlCnCTIC^C^CJIC^OlOlCJlCJlCnCJlCTlCTlCilCJiCnC^CTICri action \ aw
03 OQ OJ
5 ojwwwh-wojM^wwH-MMCjirvoMW^^-^oiw

OlCDOlCOh^ Ol h*-M>-<!COCn COO5H*. i^
1 1 1 1 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 3 S3
H
o o.^
- *
* Comments
L i terature
3* O1 ^ M
Homogeneous Reaction Kinetics
302.402
i
(D o
Scti i fe = A ~ CO L_
3 vO v ifS1
o -o E ~ K X 10 A Q x io n 3
Amount of c s c
No. React! on Solvent i_ 0 aJ
Addend tr - E L.
O g
"Sc o
react ant => -a E O
Q.
E O
1 * i^I O fe 0
<D (D n r n
d t _J
Q

.81 p-C H OC H D + H* CH COOH A~ 2. 5 H SO -MD.25 fe F 100 4.0 -4


2564 3 ( )
2 4 A

.22 p-CH CH CH OC H D + H+ CH COOH A 2. 5 H SO -MD.25 feFA 100 4.0 -4 ( 14>


^ 32264 3 2 4

.23 p- (CH ) CHOC H D + H+ CH COOH A^-5 H SO ^0.25 "A 100 7.4 -4 (")
32 64 o 2 4

.24 p-C H OC H D + H+ CH 0 COOH not stated feF 100 4. -4 ( 14>


^6564 3 H 2 SO
4 A *

.25 2, 3,4-(CH 0)- C H T + H* H 0 A < 0.04 KHSO, 0.50 feF 25 1,84 -7 f 21 )


3 362
1.00 25 4.4 -7
2.00 25 1.05 -6
2.50 25 1,44 -6
CHC1 COOH 0.12 25 3,4 -8 CO
CJi
0.24 25 4.8 -8 XI

1.21 25 1.51 -7
2.42 25 2.40 -7
4.84 25 6.0 -7
7.24 25 1.10 -6
12.13 25 1.23 -4
CF COOH 0.99 25 4.8 -7
3
2.16 25 1.22 -6
4.04 25 5.0 -6
6.73 25 1.37 -5

.26 2,4,6-(CH 30) g C 0H 2T + H+ lo^i.s [CH COOH] = [CH cc)ONa] 0.01 k\ .3 -7 (">
V *
* 0.025 ^25 3.8 -7
0.05 ^25 4.5 -7
0.1 ~25 9.3 -7
strong acid 0.05 4 -4

National Bureau of Standards - National Research Council


December, 1957
z
03 03 03 03 JS 5S ^a o
03 ro -* 8 CO 00 <3 o
^ * 03 ro
1
^333 A A o a^
o ffi ^ 9V
ko o o +
M 10 10
+
, X
K
5>
sc
X
as w
.'''
g r 8
w W 03
O 0
^^
+ o
3
l
CO
25 25 ffi Sol vent
O 0 N 0 0*
CO CO CO 63 W 63 O
CO
3! tbenzltutened
PD S ^
>
3
P ? ? *
ro ro ro jo
oi 01 01 cri 1
cn ct
tan
eac
r o
Amount
0000
O) CO GO Op 5*
o o o o to "" -h
^
Oi Ol O5 Ol O
d- a
10
II
V*
D3 0> W roc00300,-0303
(ft 2
izene
"V *+ *+ *+ Addend
3
Amount of
II II II II
tfl t3d Cd td addend
O
Def i ned mass-
>^ >^ action law
>^ " >^ ^
1 1 1 1 en rorororotNDforoiNDro ococo-vj Temperatu re
O3 03 03 03 g o oiuioioicnoicnoiui ooioco
03 03 03 03
v 03 h-*- (-* M^ oiroH^tf^cn^i* ro i oi ro
3&*
O3t-k OOOO3aiO^OO> i^M ^
II
1 1 1 1 i i i i i i i i i i i i i i i 3 O
CO CJ1 rf^ H-
8 *
* ^o ^
II
^ 3 o
# * * * X- -X- * # Comments
*1 -J -* 10 ^^ ^ r- L i terature
'"^l
6S6T
Homogeneous Reaction Kinetics
302.402

k A
ij i* rera
tu
Temp k x 10n A x \Q n Comments erature
L
ti
Amount
of E ~"
vent
Sol Amount of Addend addend
No. React i on -o c S
a, o
reac tan t c fe n A n
. o
<D i
0

K4" =B ^-33 "7 C7)


.35 3-F CC H D + NH ~ NH 3 A=0.25-0.e;B=0.6 feFA 1 *
364 2
K+ - B '^-33 -3 (7)
.36 4-F 3 CC 6H 4D + NH^ NH, A=0.25-0.6;B=0.6 * FA 1 *

.37 2-HO-5-C1C H -1, 3-D + H* 10 2A-2. l;wt. % H 2 S0 4 =40.5 ftFA 25 1.57 -7 *


( 3)( 5)
62 2 V -7
47.0 25 4.73
53,0 25 1.59 -6
59.0 25 5.32 -6
63.5 25 1.59 -5
wt. % H PO = 63.6 25 1.17 -7
68.1 25 2.67 -7
CH-

72.7 25 5.6 -7
76.4 25 1.48 -6

Anthracene

9 ' 10- D 2C 14H 8 + H+ H 8 Wt. % H 2 S0 4 = 84.0 CC1 2x vol. feFA 25 5.2 -4 *


(8)
.38 4
85.0 25 1.0 -3
85.9 25 1.7 -3
87.8 25 4.3 -3
90.0 25 2.3 -2

COMMENTS
General: For general treatment of Isotope exchange reactions see ( 8 ). in all cases where defined mass action law Is given
as feFA the first order Isotoplc equilibration Is given as the rate constant. This Is calculated from the fractional ex
change, X, at time, t, by the equation fe=-l/t Zn(l-X). The rate constant for this may in special cases be a pseudo first
order rate constant for the actual exchange reaction. For example this occurs if the reverse reaction is negligible due
to an unlimited supply of one isotope from the solvent. It should be noted however that such a rate law has not been con
firmed as being pseudo first order so long as dependence of exchange rate upon concentration of reactant has not been de
termined.

National Bureau of Standards- National Research Council December, 1957


Homogeneous Reaction Kinetics
302.402

Reaction: (.4) First order rate constant only for isotopic times the volume of liquid. (.11) First order rate con
equilibration, fractional exchange. (.4.1) Calculated stant for isotopic equilibration. (.12) Rate law is for
first order constant for rate of isotopic equilibration from exchange of deuterium with rinq hydrogen. Dependence of
relative value of ( 17) combined with deuterium exchange calculated rate constants upon hydrogen concentration of
rate of ( 4). (.5) Pseudo first order rate constant for medium may be expressed at 100C by:
reaction as written since reverse reaction eliminated by log fe= 1,26 log[H + ] -4.68
rapid exchange between NHD" and solvent. (.5.1) or using an average activation energy of E = 27.3 the
First order rate constant only for isotopic equilibration, Arrhenius constant A - 2.2 x 10 ll [H+] 1 ' 26 ' (.14)
fractional exchange. (.6) Rate constant for first order First order rate constant for isotopic equilibration. Log k
isotopic equilibration only, value in 81.8 wt. % Hg S0 4 observed to be linear function of Hammett's acidity func
calculated from relative rate of ( 17) and rate for tritium tion -H Q with slope of 1.08 in H SO solution and slope
exchange (.6.1) of ( 18). (.6.1) Rate constant for first of 1.42 in HC1 solution. (.15) First order rate con
order isotopic equilibration only, calculated from time vs. stant for isotopic equilibration. (.16) First order rate
CO
relative activity data of authors. (.8) Rate constant constant for isotopic equilibration for less than 25% reac Oi
CO
for first order isotopic equilibration only. Value for 81.8 tion due to side reactions producing precipitate and dark
wt. % H gSO 4 calculated from relative rate ; 17) with rate coloration, It was impossible to obtain isotopic exchange
for tritium exchange (.8.1) of ( 18). (.8.1) Rate con data in H 2O-H 2S0 4 medium. (.17) First order rate
stant for first order isotopic equilibration calculated from constant for isotopic equilibration. (.24) Concentra
time vs. relative activity data of authors. Simultaneous tions of reactants not stated but probably the same as
sulfonation to extent of about 5% of the exchange observed. (.21)(.22) and (.23). (.26) Temperature not stated but
(.9) Rate constant for first order isotopic equilibration assumed to be room temperature. (.27) Rate data is
only. (.9.1) Rate constant for first order isotopic only for exchange of ring hydrogen. (.28) Authors ob
equilibration calculated from time vs. relative activity serve that log k is linear with Hammett's acidity function
data of authors. (.10) Isomer distribution determined H with a slope = 0.94 up to about 85% H 2S0 4 . Rate of
by ( 17) and kinetic data by ( 1). In absence of catalysts sulfonation observed to be slow compared to exchange.
results erratic and first order rate constant estimated to be (.29)(.30) Rate constants based on no more than one or
less than 10~6 sec." 1 at 140C. In presence of NO as two point determinations. (.31)(.32)(.33)(.34)(.35)(.36)
catalyst HC1 was lost to extent of 1.5 to 2.3 times the Rate constant for isotope equilibration is pseudo first or
amount of catalyst. No correction made for portion of reac- der rate constant for reaction as written since reverse
tants in vapor phase. The volume of vapor was from 5 to 10 reaction is negligible due to large excess of protons in

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.402 10

COMMENTS

solvent and rapid exchange between solvent and NH 2 . acid solution. Concentration of A in CC1 layer = 0.1 M/l.
(.37) Authors observe that log k is linear with Hammett's Rate of stirring showed no appreciable effect. Initial rates
acidity function H with slope = 0.90 in H 2S0 4 and 1.00 are listed as rate of exchange increased with progress of
in the H 3P0 4 solution. (.38) Reaction carried out in reaction. Authors attribute this to increase in solubility
two phase system of 2 volumes of CC1 4 to 1 volume of of A in acid layer as parallel sulfonation proceeds.

Co
LITERATURE
(*) A. E. Comyns, R. A. Howald, J. E. Milliard, ACS 1956, 78, 3989. O V. Gold, F.A. Long, ACS 1953, 75, 4543.
( 3) V. Gold, D.P.N. Satchell, CSL 1955, 3609. ( 4) V. Gold, D.P.N. Satchell, CSL 1955, 3619. ( B) V. Gold, D.P.N.
Satchell, CSL 1955, 3622. ( 6) V. Gold, D.P.N. Satchell, CSL 1956, 2743. ( 7 ) G. E. Hall, R. Plccolllni, J.D. Ro
JO
berts, ACS 1955, 77, 4540. ( 8 ) G.M. Harris, TFS 1951, 47, 716. ( 9 ) M. Kolzuml, Bull. Chem. Soc. Japan 1939, 14, Cn
XT
353. ( 10 ) M. Kolzuml, T. Tltanl, Bull. Chem. Soc. Japan 1938, 13, 681.
( ll ) M. Kolzuml, T. Tltanl, Bull. Chem. Soc. Japan 1939, 14, 40. ( 12) M. Kolzuml, Bull. Chem. Soc. Japan 1940,
15, 37. ( 13 ) A.J. Kresge, Y. Chlang, ACS 1959, 81, 5509. ( 14) W.M. Lauer, J. T. Day, ACS 1955, 77, 1904.
( 15) W.M. Lauer, G. W. Matson, G. Stedman, ACS 1958, 80, 6433. ( 16) W.M. Lauer, G. W. Matson, G. Stedman, ACS 1958,
80, 6437. ( 1? ) L. Melander, S. Olsson, Acta. Chem Scand. 1956, 10, 879. ( 18 ) S. Olsson, L. Melander, Ada. Chem.
Scand. 1954, 8, 523. ( 19 ) D.P.N. Satchell, CSL 1956, 3911. ( 20 ) D.P.N. Satchell, CSL 1958, 1927.
/22
D.P.N. Satchell, CSL 1958, 3904. (**) D.P.N. Satchell, CSL 1958, 3910. ( 23) A.I. Shatensteln, N.M.
Dykhno, E.A. Izrallevlch, L.N. Vaslleva, M. Faivush, Doklady 1951, 79, 479.

National Bureau of Standards - National Research Council December, 1957


Homogeneous Reactions ISOTOPE EXCHANGE Liquid phase
302.403
H-D exchange on C in heterocyclic ring Amounts are tn M/I.
Rate constants are
In gram atoms/1 and
sec., fractional
times In sec.
under rate law indicates rate constant Is for pseudo first order rate of Isotope equilibration
k "ion
fmainsed 1,0 v
Amount
of femperature K x
c addend actlawion
Amount of
No. Reaction Addend P H *
reactant
o n
CO

.1 CH N+-CCH + H 0 > CH N^-CCH + HOD H 0 A = 1.1 Phosphate buffer, 0.02 5.37 feF ~25 1,400 5 -4
Br =A
D-6 'CH H-C CH

(3j ^ dl met hy ! t hi o zo ! 1 urn bromide)

.2 C H CH N^-CCH + H 0 > C H N^-CCH + HOD Ha A = 1.1 Phosphate buffer, Br~ 0.02 5.37 feFE ~25 450 1.5 -3
6 5 2 I. 3 2 y 3 6 5y

I>C CH H-C1 CH
S S

(3-benzyl-4-methyItMozollum broml de)

COMMENTS
Exchange followed spectropho tome trie ally In the Infrared using 0-D
bond at 3.98^6 and Beer's law followed In the region 20-80% transmlttance.

LITERATURE
R. Breslow, E. McNelis, ACS 1959, 81, 3080.

National Bureau of Standards - National Research Council December, 1958


Homogeneous Reactions
Liquid phase
302.461 ISOTOPIC EXCHANGE Amounts are In M/I.
Oxygen exchange on carbon Rates and rate con
stants are in gram
atoms/I and sec.
Coded solvents at
end of tab Ie.
R under rate law Indicates that constant listed Is the rate of the chemical process responsible for exchange ( 15).
feF under rate law Indicates that rate constant is for pseudo first order rate of isotopic equilibration.

0) i
c k = A = 0
w * C t-
-H 0* -H "-" L_ fe x iQn A x I0n GO 3
c z: c E Amount of e ~~ c -*-1
0) Amount of -M
No. ErH React! on o Addend -o c cd i E
0) IT> 0)
20>
0> 0 reactant addend c - 0)
CLr-l d. O
00 "C' fe A* O
Q. 'C E n n 3
3 <D J 05
CO H-
Q

.2 n-C 4H9OH + H g0 18 B A=0.73 H 8 S0 4 0.046 , FE 125 7 -8 c13)


0.46 5.6 -7

.3 C H (CH )CHOH + H O 18 B A=0.8-1.6 HC10 0.111 feA 101 6.7 -7 *


(8)
253 2 4
0.176 101 1.08 -6
O.E84 101 3.2 -6
0.44 101 5.1 -6
0.70 101 8.6 -6
0.91 101 1.25 -5
1.15 100 1.09 -5 (9)
2.35 100 3.4 -5
3.40 100 8.6 -5
4.10 100 1.34 -4

.4 (CH^COH + H^ 18 B A=1.04 H 8 S0 4 0.045 fe F E 55 1.33 -5 ( 13 )


0.45 55 1.54 -4
0.045 75 1.97 -4 30

.5 (CH 3 ) 3 CCH 3OH + H 80 18 B A=0.242 H2 S 4 0.48 feA 125 1.4 -8 ( 12)

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.481

03 0
C J> <D fe = A *
+- -M '^ 3 5 3 k x 10^ ,4 x I0n -H 3
*>
c o E C
O z O D Amount of Amount of rt <D Of
No. > ~
-o c
E _, Reaction Addend <D S
* in c *~ CL -H
O ^ reactant addend 0
'C " E fe >! 0 O
ex. r~' W i (D n n _J
3 H-
CO Q

-5 ( 14)
.6 C 6H 5 (CH 3)CHOH + H 20 18 B not stated HC10 4 .02-. 08 feA[H+] 30 1.07 *

54 3.3 -4 28 3 15

A~l -7 (7)
.7 (CH 3 ) 2 C(OH)C(CH g) 2 OH + H 2 0 18 B H a S04 0.05 feFE 73 9
1.6 73 6 -5
2.1 73 7 -5
5.35 73 5 -4

A=-O.UB^ HC10 4 0.101 feA 25 8 -5 *


C 10)
.8 4-CH OC H (C H )CH0 18H + HO D160*
36460 2
0.265 25 3.8 -4
0.394 25 7.5 -4
0.936 25 1.04 -3
D140* A^0.02;B^33 HC10 0.35 25 1.2 -3
CD
4
0.63 25 6.7 -3

Carbonyl oxygen
.9 CH 2OH(CHOH) 4 CH0 18 -f H gO B A ^1- 1 buffers PH-7.0 *FE 40 1.0 -5 *
( 17)
7.0 50 2.8 -5
7.0 61 1.03 -4 23 2 11
8.1 61 2.3 -4
6.5 61 8.8 -5
6.0 61 4.4 -5
5.0 61 1.88 -5
3.4 61 1.92 -5
2.8 61 2.5 -5
2.1 61 1.05 -4
1.5 61 2.9 -4

National Bureau of Standards- National Research CouncM December, 1959


Homogeneous Reaction Kinetics
302.461

05 k = A =
C J, * o
CO * k x j_o r x ion CO
-H 3 D

c O Amount of Amount of E c
a> ^ s5 CD
No. e z React! on Addend -o c E
CD O CD O
reactan t addend E
0 C Q_ 0
ITS k A
CO ^ E O
H- O CO n n 3
H-
CO o

(11)
.10 (CHJ
x 3 2 CO 18 + H 2 0 A B^5. 5 sallcylate buffer feAB *
10 3 [acld] = 1.97 10*[salt] =0.98 25 2.5 -6
1.99 9.92 25 2.4 -6
5.0 1.00 25 6.5 -6
10.4 1.01 25 1.35 -5

Oxygen of carboxylic acid


I 1 ")
.11 H 8C 80 4 H- H 20 18 B 10 3A=2.6-92 HC10 4 . 002- 1 feA+fe'A[H^] 25 fcFl.23 -4 * i?
25 fe'=7.3 -4

10 2A=5.6-10 HC1 0.09-0.5 80 2.4 -4 * ( 1B)


i
.12 .1 C H CO OH *^" H 0 B fe A [E+]
60 2 -4 (") c-t.
D133* 0.07 80 1.6

(') O
.13 >-CH aC6H 4COOH + H.O" D133* not stated HC1 0.069 feAtH4! 80 1.5 -4 *
feAtH 4"] -7 ( B)
.14 2,4,6-(CHj C H COOH + H 2 0 18 D133* not stated HC1 0.069 80 1.5 *
3362

-4 f 0\
.15 -CH OC H COOH + H O 18 D133* not stated HC1 0.064 kA\#+] 80 1.00 *
r 3 6 4 2

.16 m-CIC H COOH + H O 18 D133* not stated HC1 0.064


feAtn4"] 80 1.77 -4 * r^
64 2

.17 -ClC H COOH + H O 18 D133* not stated HC1 0.064 feAfe4] 80 1.1 -4 * ()
64 2

Oxygen of alkyl ester


10 3A=l-7 HC1 1.0 feA 99 7.5 -6 * C 1)
.18 C H C0 18 OC H + HO B
66 20 2 ( 3)
D133* 10 2A-1 0.01 fe A [H+] 25 6.2 -8

10 3A=10 3B=l-7 Na+ =B -3 * (1)


.19 H + OH" H 0 feAB 25 6.3
H co 18oc 20
c 60
10 SA=10 2B~i 9 1.8 -4 ( 3)
D133*
25 7.8 -4 ( 1) ( 3)
40 2.6 -3 14.9 6 7 (3)
National Bureau of Standards - National Research Council December, 1,959
Homogeneous Reaction Kinetics
302.461

O) fe = A -
c 6
^_, * * u fe x 10n A x ion CO
3
c c | Amount of Amount of e -~ 4-> -H
c
No. 1 React Ion > ' Addend L. E o 2
* m "S o ID E 4)
reactant addend Q.
E -H
CO ^ 0
E fe A o
t n n _J
3 h-
CO Q

.20 C H C0 18OCH(CH ) 10 3A=10 3B=l-7 Na+ = B feAB 2.3 -3 C 1)


+ OH" H 0 25 *
65 32 2*
D133* 62 4.9 -3

.21 C H C0 18 OC(CH ) + OH" 10 3A=10 aB=l-7 Na+ = B feAB 62 1.7 -4 * C 1)


D133*
65 33

M20* 10 3A=10 3B^5 Na+ = B -3 C 4)


.22 C H CH.CH 0 C0 18OCH Q + OH" feAB 25 1.46 *
O O f> O

M30* 10 3A=10 3B~5 Na+ = B -4 C4)


.23 C H CH CH CO 18OC H + OH" feAB 25 8.5 *
6522 25

.24 2,4,6-(CH 3 ) 3 C6H 2COOCH 3 + H 20 18 D160* 10A=2 feA 126 1.5 -2 * (2) I
.25 C H CH CHNH C0 18OC H 10 2A=1.5 Cu++ 0.0774^1 feA 25 7 -4 * () O
+ H 0 B
652 2 25 2
buffer PH=7.3 f

.26 C H CH CH(NHCOC H )C0 18OC H M50* 10A=10B~3 Na+ -B feAB 25 3.0 -2 * (4)
+ OH*
652 65 25
Oxygen of amide
A=B=0.1 Na+ = B 7.6 -5 (3)
.27 CAH H 20 feAB 41 *
o O
RC0 18NH *0 + OH"
80 1.87 -3
109 1.26 -2 17,5 1.2 8

CODED SOLVENTS
D133*(40), (60) Dioxane volume % Indicated + H gO

M20* (30), (50) Methanol volume % indicated + H 20

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reaction Kinetics
302.461

COMMENTS

General. For general treatment of isotope exchange reac law not confirmed as concentrations of A and B not varied
tions see ( 15). In all cases where defined mass action law
Rate constant expressed by authors in terms of catalytic
is given as AF E the pseudo first order isotopic equilibra constants, k = A [acid] + k b [base] + ^ H [H*L where
tion constant is given as the rate constant. This is calcul
k a = 1.14 x 10"* A b = 2.5 x 10" e , k E = 1.95. Reaction
ated from the fractional exchange, X, at time, t, using the found to be too sensitive to catalysis by both H* and OH"
equation k ~ -lAZrc(l-x). In cases wnere the reverse ex
to measure directly in absence of a buffer. (.11) Rate
change is negligible due to a large excess of one isotopic
law calculated from only three observed points is based
species this might be equal to a first order rate constant
on calculated concentrations of species indicated not on
for the reaction but this is not verified unless exchange
total stoichiometric concentrations. (.12) Addition of
dependence on reactant concentration has been determined 0.09 N KC1 caused no significant change in rate. Either
In most cases where rate constant for the chemical process
reactant labeled initially. (.13)(.14)(.15)(.16)(.17) Rate
responsible for exchange has not been explicitly deter law with respect to H* not confirmed experimentally but
mined the value listed under k will be indicated in the
assumed by (^. (.18) Rate constant calculated from
"Defined mass action law" column by R, where R is the
pseudo first order rate constant of simultaneous hydrolysis
rate of the chemical process responsible for exchange, see
reaction and ratio of hydrolysis rate constant to exchange
co
rate constant determined experimentally. (.19)(.20)(.21)
Reaction. (.3) Selected values. ( 8) labeled oxygen in (.22)(.23) Rate constant calculated from second order rate
either A or B, also observed that racemization reaction constant of simultaneous alkaline hydrolysis reaction and
twice as fast as exchange. ( 9) plotted log k vs. -HQ/ ratio of hydrolysis rate constant to exchange rate constant
Hammett's acidity function and obtained a straight line determined experimentally. Authors use data to calculate
rate constants for intermediate steps in their proposed
with. slope of 1, at [HC10J >0.6. (.6) Rate constant
for exchange reaction about 20% smaller than rate con- mechanism of hydrolysis and exchange. (,24)(.25) Rate
constant calculated from pseudo first order rate constant
for racemization reaction corrected for simultaneous elimi
of simultaneous hydrolysis reaction and ratio of hydrolysis
nation reaction. (.8) Rate law with respect to A not
rate constant to exchange rate constant determined experi
verified as [A] constant. Rate of exchange and rate of
racemization essentially the same. mentally. (.26H.27) Rate constant calculated from
(.9) Buffers used
were barbituate, phosphate, acetate, phthalate, HC1-KC1, second order rate constant of simultaneous alkaline hy
and oxalic acid. drolysis reaction and ratio of hydrolysis rate constant to
(.10) Selected data. Second order rate
exchange rate constant determined experimentally.

National Bureau of Standards - National Research Council


December, 1959
Homogeneous Reaction Kinetics
302.461

LITERATURE

t 1) M.L. Bender, ACS 1951, 73, 1626. / 2) M. L. Bender, R. S. Dewey, ACS 1956, 78, 317. ( 3) M.L. Bender, R. D.
Ginger, J.P. Unlk, ACS 1958, 80, 1044. (*) M.L. Bender, K. C. Kemp, ACS 1957, 79, 111. ( 5) M.L. Bender, R, R.
Stone, R. S. Dewey, ACS 1956, 78, 319. ( 8) M.L. Bender, B. W. Turnquest, ACS 1957, 79, 1889. ( 7) C. A. Bunton,
T. Hadwlcfc, D. R. Llewellyn, Y. Pocker, CSL 1958, 403. ( 8) C. A. Bunton, A. Konasiewiqz, D. R. Llewellyn, CSL 1955, 604.
() C.A. Bunton, D. R. Llewellyn, CSL 1957, 3402. ( 10) C.A. Bunton, D. R. Llewellyn, J. Wilson, CSL 1958, 4747.
( 1X) M. Conn, H. C. Urey, ACS 1938, 80, 879. ( 12) I. Dostrovsky, F. S. Klein, CSL 1955, 4401. ( 13) I. Dostrov- CO

sky, F, S. Klein, CSL 1955, 791. ( 14) E. Orunwald, A. Heller, F. S. Klein, CSL 1957, 2604. ( 15) O.M. Harris,
TfS 1951, 47, 716. ( 16) R.M. Mllburn, H. Taube, ACS 1959, 81, 3515. ( 17 ) D. Rlttenberg, C. Oroff, ACS 1958,
80, 3370. ( 18 ) I. Roberts, H. C. Urey, ACS 1939, 61, 2580, 2584.

National Bureau of Standards - National Research Counctj December, 1959


ro ^ O
o a I
CO ^
"-" a
CO O
CO O CO
CO
sjr"
1 "*J M*"^"
M to
+ -H +
=? ^ "f 2)
o o 0
O a *. f
a _ w o
CO o
CO 3

a
i i Sol vent
M- H* t-*
(Medium*)
(_k (->
tl H It O O (D
X
dd dd dd do !> 3- 5
II II II II II 8 ! Q O
o O O )_.-
1 - O
b o o co en r- _^
o> ed ' o a- "^
en ^ en " ^
2. n
^ ^ ^ I rn
X
I 888 Addend 3(D n
a a a a
o
b
? 8 ? S. o
o OL c - o
b 8 T 8 <B 3
o> D ^
to o ro o ** Q. 0
5 m
-K
- Q
0
3r po a Q.
1' a* ?r
> H > >
O CA ^0 O O
a 0
i \ J ' 1
o L-J l-J tt 9
< CO
1I 'P
M- (-
jooococo c^toM-o wrof-^ow
en enenoenen enenen enenen en Temperature
W
Oi o o
ro X
X H* ii
I 1 1 1 1 1 1 1 1 I 1 1 1 1 h 3 3
I\3 5? ,
W .
3 P 3
. o o^ H- O
(o a c
o H- -a
5 a 53 " 5 1.
CO (B X,
-- -1
j a ^
* Comments
3.- r
. tfi 3 to
9 P>
3- H* H* Li terature 3 T
a. o
Homogeneous Reaction Kinetics
302.466

^-
k = A =
-H ^ T3 ^ fe x lQn A x i0n ^
c Defined mass- H C -M
c 3 Amount of <d p o> (d
No. Reaction .- Addend c ^ I- A E u
> ~ reactant 3 ^ action law <D E 0)
Q. o *-
&l |- 1 fe n >4 0 n "

.4 (C 6H 5S*> 2 + C eH oSH MW 12* A = B = 0.0375 NaOH 0.0025 feA[oH~"] 0 4.6 -2 f 1)


15 2.0 -1
25 4.9 -1
35 1.3 0 15.8 2 11
Co

CODED SOLVENTS
^
MW12* CH gOH + H gO (12%) CO
en
co
COMMENTS
General: For general treatment of Iso topic exchange reactions see ( 2).
Reaction: (.1) Rate law verified by variation of concentrations of A, B and NaOH. Rate constants calculated by dividing
exchange rate, R = -- *~~ ln(l-xJ, by A and [NaOH]* A and B represent concentrations of reactants and X Is fractional ex-
tent of exchange at time t. Authors suggest mechanism Involves direct reaction of thlol Ion rather than catalysis by OH~.
Since [OH"] <B the [OH~] y [n-C^S"] ' (.2) Rate constant not calculated from R since [OH~] >B and authors do not give
sufficient proof of rate law to validate such a calculation. Value of rate constant listed was extrapolated to 25 by auth-
ors and at best only gives order of magnitude.

LITERATURE
C 1) A. Fava, A. Illceto, E. Camera, ACS 1957, 79, 833. ( 8) O.M. Harris, IPS 1951, 47, 716.

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reactions ISOTOPIC EXCHANGE Liquid phase
302.474 Halogen on IVth group halides Amounts fn M/I. Rate
constants in M/I and
sec.

k = A =
A x I
Amount of
No. Reaction So I vent -o c
Asf
a, o
reactant

.1 Snd + Sn Cl -> Sn*Cl rt + snCl G H OH 10A=2-10; feAB 25 6.0 -5


2 5
29 1.04 -4

36 2.31 -4
42 5.3 -4 24 13 fie

COMMENTS
Reaction homogeneous as addition of glass wool and pyrex helices did not effect rate.

LITERATURE
E.G. Meyer, M. Kahn, ACS 1951, 73, 4950.

National Bureau of Standards - National Research Council December, 1959


Homogeneous Reactions ISOTOPE EXCHANGE Liquid phase
302.477 Halogen for halogen, in organic compounds
Reaction types: RX RX + X" Amounts are in M/I.
Rate constantsarein
(A) (B) (L) (M)
M/I and sec.
RX RX* + i

A = concentration of A + L and B = analytical concentration of B + M unless stated otherwise


01
CO k =
c CO t V) ^ =
ID
cd cd n o 71 CO
K
E
fe x** m
JJJ CO
o> z Amount of Amount of Id c M
T3 C L. 0 cd
No. 1 ^ R e ac t i o n Sol vent Addend CO O S
d>
^ react ant addend C CD
Ou i -M
- rH **- o AJ A
Q. i n n cS
<o cd h- _J
o

Saturated Alkyl Hallde

L1+ = B -3 -6 (*) CO
.19 CHgCl + d*~ (CH 3) 2CO A^0.3; B^0.03 h AB 1.09 01
25 3.88 -5 01

45 3. 18 -4 20. 1 2 10

CH Br + Br*~ Ll+ =B -31 -4 <>


.20 (CH 3 ) 2CO A = 0. 15-0.2; fe AB 2.68 *
3
-25 6.30 -<?. ;
B = 0.024
-18 1.46 -2
-11 3.40 -3 IR. 8 5 10

Ll+ = B -7 ( 2)
.21 P H PI -4- PI (CH 3) 2CO A^O.2; B^0.03 ftAB 25 5.5
40 3.09 -6
60 2.40 -5 21.5 3 9

Ll+ =B -11 -5 ( 8)
.22 2H 5Br + Br*~ (CH 3) 2CO A^O.2; B=0.024 feAB 2.89 *
0 1.06 -4
8 2.76 -4

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
302.477
A = concentration of A + L and B = analytical concentration of B + M
en
c k = A - 0
Def
i
nedmass 1
Temperature 1
Comments u
acti
1awon k x 1071 3
Amount of Amount of -M
0 2
No. React i on So 1 vent S OS
Addend
In react ant addend
" rH
Q. n n -J
CO

.22 Ll + = B -4 ()
C 2 H 5 Br + Br*~" (continued) (CH 3) 2CO A^O.2; B=0.084 k AB 16 6.62 *
25 1.70 -3 17.5 1.3 10

.23 .1
W + x*~ Na+ = B 25 8.0 -5 * ( 7 )( 8 )
CH 3OH A = 0.04;
10 4B = 2-70
C 2H f5OH A=0.9; B=0.14 kAB ao 1.08 -4 * ( 81)
-4 CO
0.9-4 0.017 30 4.3
0.030 30 4.4 -4
0.075 30 3.4 -4
-4 CO
0. 15 30 3.3
0.6 30 2.3 -4 05
1.5 30 2.2 -4 -
0.9 0.14 40 9.0 -4
0. 14 50 3.2 -3 19 K*
-3 * ( 88 ) CD
A=0.02J B=0.017 50 2.89
60 7.81 -3
70 2.07 -2 21.3 7 11
-27 -4 (*)
(CH 3) 2CO A^O.3? B = 0.10 1.23 *
-17 4.90 -4
- 6 2.18 -3 17.4 3 11

n-C 3H ? Cl + Cl*~ Ll + = B -6 * ( 37 )
.24 (GH 3) 2CO A^O.l; B^0.03 kAB> 44 4.21
(CH 3) 2co + ao% CH 3N0 2 44 1.73 -6

Ll + ^ B -7 ( B)
.25 (CH ) 0CHC1 + Cl*" (CH 3) 2CO A= 0. 2; B = 0.028 feAB 60 4.55
O t&

Na-H ( 28)
n-C H Br + Br*~ TJ f\ = B -5
.26 .3 H 3 A = B = 0.1 kAB 35 2. 13
3 7
61 2.13 -4
79 8.4 -4
100 3.6 -3 18

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
302.477
A = concentration of A + L and B = analytical concentration or B +
o> CO A =
c CO * 4) /e =
l_ V
0) Cti CO
e 3 fe x I0n ^ x lQn -f-1 3
1 5 Am o u n t of Amount of 3 c -H
-a c L. S <D 05
No. E r-l React i on So 1 vent Addend 03 0
0 E L.
* ir> reac tan t ad dend c Q. E 0)
"^ ^ E k >4 0 4-1
n~ o 10 n n cS
Q- 03 05 (
O _J
C3

.26 Li+ = B .7 -5
.3 *
7
n-c 3 HLBr + Br*~ (continued/1 (CHJ SCO A=0.16; B=0.024 k AB 3.30 (3)
15 4. ID -4
25 1.08 -3 ( B)
31 1.91 -3 17.5 6 9
( 3)
CO
O^0 , B = 0.024 wx = B k AB 25 2.4 -4 (8)
Ll+ B k AB 5.07 -5 *
(8)
.27 .4 (CHJ CHBr + Br*~ (CHJ 2CO A^O.2; B=0.024 35
3 2
0.024 42 1.05 -4
0.024 90 2.46 -4
0.017 58 5.30 -4
0.024 58 4.67 -4
0.060 58 3.6 -4 CO

0.024 65 9.74 -4 19.7 5 9

(CHJ 2CO A=0.1; 10 3 B= 5-50 k'aAB 30 4.86 -5 *


( 16>
40 4.43 -4
(a = degre e of dlssoc latlon of LlBr) 60 2.95 -3 20.0 4 10

n-C 3H ? I + I*-
Na+ =B h AB 35 3.7 -4 *
(21>
.28 .7 WH A=0.75; B= 0. 14
n n 45 9.4 -4
50 1.95 -3 *
( 28)
0.02 0.017
-3 ( 21)
0.75 0.14 55 2.35 15
0.02 0.017 60 5.33 -3 (28)
n n 70 1.36 -2 20.8 2.5 11

.29 .8 (CH 3 ) 2 CHI + I*" CtH BOH A=0.02j B=0.017


Na+ =B k AB 45 5.6 -5 *
{28)
60 3.42 -4
70 9.6 -4 23.8 1.4 12

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
302.477
A - concentration of A + L and B = analytical concentration of B + M 4
A 0
Supp
ting
1emen 1951
No. Defmassined Temp
atureer v
k x K A4 * Comments 3
Amount of Amount of law
i
tacon
No. R e a c t i on Sol vent Addend i 0)

reactant addend 0
n A n
I

.29 .8 (CH g) 2 CHI + I*" (continued) Na+ = -B -5 ( ,i,


WH A- 1.63 B=0. 14 k AB 45 6.4 *
55 1.04 -4
60 2.6 -4
70 7.0 -4 30.5 7 9
(CH 3) 2CO A = 0. 12; B = 0. 1 Na+ = B 0 -5 ( 4)
2.93 *
25 5.87 -4 19.4 1 11
CO

.30 C 0H (CHJCHC1 + SnCl * "~ C 7 H 16 A = 0.06-0.47; k AB/ (K + A) 160 3.8 -6 * ( 13>


O 0 4
6 = 0.008-0,065 3DO ~ 1 -4
Ofc
160 K= 1.5 -1 3
00

.31 .10 n-C H Br + Br*~ (CH 3) 2 CO A = 0.04; 10 4B=0. 5 LI* = B fe AB 26 3.93 -3 * ( 7 )( 8 )


2.5 26 3. 13 -3
17.1 26 2.56 -3
"
79 26 1.44 -3
Oi
191 26 1.07 -3

.32 (CH ) CHCH Br + Br*~ Ll + = B -5 ( 3)


32 2
(CH 3) 2CO A = 0. 14-0. 17; feAB 25 5.82 *
B = 0.024 33 1.40 -4
42 3.43 -4
50 7.04 -4
58 1.44 -3 18.9 4 9

.33 . 13 (CH 8) 3CBr + Br*' Ll* = B -6 ( 8)( 8 )


(CH 3) 2CO A=0.16; B=0.024 fe AB 25 5.26 *
5 ( 3)
40 3.03
49 8.46 -5
60 2.58 -4
71 7.35 -4
79 1.46 -3 21.8 5 10

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
302.477
A = concentration of A + L and B analytical concentration of B + M
ing
ement
1
Supp k = A
No.
1951 Defmainesd 1aw
act
ion Temperature k X 1 A > ion Comments terature
Li
Amount of Amoun t of
No. React i on So 1 vent Addend
reac tan t adder d
n n

Li+ = B k AB 4.06 -6 *
(">
.33 . 13 (CHJ J2Br + Br*~ (continued) (CH 3) 800 A=0.07; B=0.05 25
3 3
35 1.50 -5
44 3.99 -5
60 1.91 -4
Ll+ = B -8 (18)
A = 0. 1; fe lA + 20 k^.6 * CO

B = 0.005-0. 1 fe 2o,AB 30 fe 25.5 -6


40 k 3. 2 -7
(a - degree of dissociation of LiBr) 40 fcVos -5
60 & 22.0 -6 19.7 1.6 7
60 k^.Q7 -4 21.8 1.0 11

-6 ( 8)
CH NO A=0.05; B=0.023 (c^y -B kk 22 2.98 *
0.012 41 2.62 -5
41 2.53 -5
0.024
0.048 41 2.88 -5
50 6.54 -5 20.6 6 9
0.022

Na+ ( 21)
= B kAB 30 1.65 -4 *
.34 n-C H I + I*~ CHOH A=0.6; B=0.14
4 9 5 4.4 -4
40
50 1.09 -3
60 2.85 -3 19
Ll+ t 11)
=B kAB 0 1.9 -4 *
CH O CN A=0.05; B=0.01
14 1.0 -3
0.05 0.01
29 4.8 -3
0.05 0.01
29 4.4 -3
0.025 0.025
48 3.0 -2 18.2
0.024 0.01
Na+ =B kAB 0 1.8 -4
0.02-0.3 0.01
14 1. 1 -3
0.05 0.01
29 4.3 -3
0.25 0.01
29 4. 1 -3
0.25 0.05

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
302.477
A = concentration of A + L and B = analytical concentration of B + M
m
n * fe = A = o
V-
(0 J CO
E 3 fe x I0n ,4 x ion
Amount of 3
Amount of J c
No. Reaction Sol vent Addend TJ c 1_ 0> (0
0 0 S E
c 07
react an t addend E O
Q.
E fe A O
H- O 0
<D tO J n n
O
_J

.34 n-C4H9 I + l*~ (continued} CH CN A=0.01; B=0.01


Na+ = B -2 f 11)
3 k AB 48 2.65 18.0 *
0.05 0.008
Cs+ = B feAB 0 2. 1 -4
0.05 0.01 12 8.3 -4
0.05 0.005 29 5.8 -3
0.05 0.008 29 5.2 -3
0.005 0.005 40 2.0 -2 18.2
Zn+ + CO
0.48 0.096 = B feAB 48 1.7 -6
0.47 0.094 60 6. 1 -6
0.46 0.092 81 3.92 -5
0.2-0.4 0.02-0.04 100 2.98 -4

0.04 0.09 122 1.25 -3 21.9
0.5 0.10
Cd4+ = B -5
feAB 2 30 2. 16
0.5 0.10 48 1.61 -4
0.24 0.09 60 5.23 -4
0.1-0.2 0.05 82 3.99 -3
-3 Oi
0.2 0.09 82 3.61 20.6

.35 n-C H I + HI* CH <I C H K feAB 49 <1 -7 * ( 10,


4 e 3 o 5
CH OH A=0.2-0.6J B=0.075 0 2.42 -6
3
0.056 25 4.5 -5
0.041 36 1.46 -4
0.107 36 1.33 -4
0.075 49 4. 14 -4 18.6 6 12
CAOH A=0.2-0.6; B=0.054 0 5.97 -6
0.010 25 1.44 -4
0.034 25 1.30 -4
0.10 25 1.15 -4
0.34 25 9.25 -5
0.36 35 3.53 -4
0.36 45 1.55 -3 19.5 1.0 14

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
3D 2.477
A concentration of A + L and B = analytical concentration of B +
CO
OT 9 o> k = A = J
J CO u (0 V-
E 3 fe x ion A :< ion H 3
-H -H
Amount of C
Amount of o c <d <D ed
No. Reacti on So 1 v en t Addend <P o u S i_
0 0}
react an t addend - Q. O
M- O E k n A n O
<D 0) 0 _J
Q h-

.35 n-C4HQ I + HI* (continued} WH A= 0.1-0. 6J B=0.10 * AB 0 7.22 -6 *


( 10 )
0. 10 25 1.56 -4
0.039 36 5. 3D -4
0. 17 36 5. 17 -4
CO
0.039 49 1.71 -3 19.4 1.0 14
C H OH A=0.2-0.8; B = 0. 10 0 7.67 -6
0.025 25 1.01 -4
0. 10 25 1.34 -4
0.34 25 1.50 -4
0.68 25 1.53 -4
0.044 36 4.30 -4
0.12 36 4.58 -4
0.076 49 1.29 -3 18.4 2 13 Or
P tl
C 12H 25H f\LJ A= 1.0; B= 0.012 25 4.83 -5
0.060 25 6.90 -5
0. 125 25 8.86 -5
0.251 25 9.70 -5
0.318 25 1.07 -4
A= 1.0; B* 0.082 feAB 0 1.19 -6
CH 3COOH
" 0.015 25 9.78 -6
" 0.052 25 1.45 -5
0.062 25 1.70 -5
0.62
25 2.81 -5
1.0 0.21
" 0.31 25 2,72 -5
36 5.55 -5
0.082
49 1.65 -4
0.72 0.047
49 2.02 -4 18.2 1.3 12
0.29 0.12

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
302.477
A = concentration of A + L and B - analytical concentration of B + M
CO
CO * k - A s
<tf (d 9
m
E fe x 1Dn A >< ion 3
Amount of Amount of c
T3 C 0 (0
No. React 1 on So 1 vent Addend * o g k_
C
e 0
reactan t addend . E *-*
*- O kQ A* O
ctf n n 0
Q _J

.36 n-C4V +iI 8* CH CN A=0.09; B = 0.02 k AB 70 5.70 -5 (")


3
0.09 0.02 81 1.25 -4
0.09 0.02 ! 100 5. 14 -4
0.04^0.09 0.03-0. D4 122 1.94 -3 17.5

.37 (CHjCHCH I + I*" Na+ = B -5 ( 81)


CHOH A= 1.4; B= 0. 14 feAB 40 5.9 * CO
N 50 1.50 -4
60 3.5 -4
70 8.5 -4 19

Na+ CO
.38 C H (CH)CHI + I*" C H OH A= 1.4; B=0.14 = B feAB 45 7.0 -5 * (">
Ho 3 2 5
50 1.22 -4
60 3.2 -4
70 8.8 -4 20.5 CO

.39 (CH 3 ) g CI + I*" CAOH A= 1.2; B=0.37


Na^ R feAB 40 9.4 -4 < 81)
(CH 3) 2CO 0.2 0.10
Na+ = B 0 6.30 -6 * (*)
0. 1-0.5 0.10 25 1.82 -4
0.1 0.1D 45 1.58 -3 21.5 1.0 12

.40 Ll+ = B -5 ( 8)
(CHj
l 0
J3CH <6 Br + Br*~ (CH,) 2CO A^O.2; B=0.024 fe AB 89 1.88 *
105 7.10 -5
116 1.61 -4
124 2.80 -4
135 5.89 -4 22.0 4 8

.41 n-C^I + I*" Na+ = B -4 ( 21}


C 2H 8OH A=0.6; B=0.14 feAB 40 5.3
90 1.36 -3
60 3.56 -3 19

National Bureau of Standards- National Research Council December, 1955


Homogeneous Reaction Kinetics
308.477
A = concentration of A + L and B = analytical concentration of B +
CO k = A =
CO * o 0)
CO (0 L. A* x ion CO k.
E - 3 fe x ion +J 3
Amount of Amount of c H
o c J 0 ctf
No. React ion Sol vent Addend D 0 L. i E L.
reactant addend a> E 0)
0 -H
Q.
*- O E fe A 0
0 (0 <D n n _J
Q J

.42 A=0.7; B=0.14


Na+ =B kAB 50 5.7 -4 ( 81)
(CH 3 ) 2CHCH 2CH 2I 4- I*- C 3H BOH

.43 A^0.2; B = 0.10


Na+ = B kAB 35 4.48 -6 * ( 4)
(CH 3) 3 CCH 2I -f I*" (CH 3) 2CO
45 1. 13 -5
CO
65 9.06 -5 22.0 1.6 10

Ll + -B -4 (34)
.44 CH 2CH 2CH 2CH 2CH 2CHCH 2Br + Br*~ (CH BOOCCH 3) 2 A=0.05; B=0.030 feAB 90 1.23 *
CO
100 2.67 -4 9
-4 <>
111 6.13
122 1.19 -3 20.2 1.3 8

-6 ( 36 )
.45 C 5H 11 (CH 3)CHI + I*" C 2H 0H feAB 25 7.7 21.8 8 10 * CO
Oi
Ll+ = B -3 (')
.46 C O H 13JCH 3 )CHBr + Br*~ (CH 3) 2CO 1D 2A= 4-5; 10 4B = 2.61 feAB 66 7.21 *
3.02 66 7.05 -3
8.61 66 4.94 -3
15.7 66 4. 15 -3
78.0 66 2.34 -3
150 66 1.53 -3
250 66 1.32 -3
700 66 8.3 -4
1400 66 7.7 -4
10 4B - 2- 1400 fe'aAB 66 1.10 -2 (a = degree of dissociation
I of LIBr)

Cyclo-Alkyl halldes

-6 (36)
.47 c>clo-C 5H9 I + I*~ C 2H 5OH A=0.2-0.5; B=0.1-0.4 feAB 25 (8.8) *
37 3.2 -5

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
302.477
A = concentration of A + L and B = analytical concentration of B + M
01
CO X
h = A =
(0 C0 CO v_
e k x ion A x io n 3
Amount of Amount of c
i1 0
No. React! on Sol vent Addend ic E J
reac tan t addend E C
._ +j
*- 0 fe A cS ^
0 CO n n
0

-5 ( 36 >
.47 cyclo-C GHQ l + I*~ (continued) C^OH A = 0.2-0.5; B=0. 1-0.4 fe AB 47 9.0 *

56 2.49 -4
64 4.79 -4 21.0 2 ID

-7 { 36 }
.48 cyclo-V H I + I*~ WH A = B = 0.30 k AB 69 2.3
6 11
80 6.2 -7 CO

90 2. 12 -6
100 5.12 -6 25.6 5 11
CC5

-5 ( 36 )
.49 cyclo-CH-i + i*" C2H 5OH fe AB 25 (1.2) 21.3 5 10 *
7 13

-6 ( 36 )
.50 c>clo-C8H 18 I + I*" C 2H 5OH fc AB 25 (2.8) 22.0 4 10 *

5jc (M) CO
.51 bicyclo-C H Cl + HC1 A=0. 16; B = 0. 1-0. 16 k AB 0 1.5 -3 *
CHC1,3 Oi
Oi
(camphene hy droch 1 or i d e)

sf: -3 * (M)
.52 CHC1 3 A=0.16; B=0. OS-0.1 ft AB 0 1.4

(camphene hydroch lor i de)

-7 ( 36,
.53 c;yclo-c 15H 29 l + i*"" C 2H ROH fe AB 25 (9.9) 20. 1 6 8 *

Carboxyl-substituted alkyl halides

1D 3A = 3-9; -3 ( 33)
.54 CH 2 ICOOH + I*" H 20 H . fl4 0.00^0.01 fe AB 25 8.7
10 3B = 3-20 60 1.49 -1 16 5 9

-4 ( 33)
.55 CHglCOOH + I s* H 2 feAB 25 5

i" -3 ( 83 )
.5, CH 2 ICOOH + I 3*~ H 20 1D 8A9; 10 3B= 1.5-3 0.0046-B ,AB 25 8

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
302.477
A = concentration of A + L and B = analytical concentration of B + M n
W k = A =
0 S <D
rt o5 A x iort L.
a fe x ion -H
Amount of e -H 3
Amount of -M
No. Reacti on So 1 vent Addend T3 C g cd
<D 0 2
05
react an t addend C 0
Q. k A n -M
0
H- O n n O
1
o at t-
0

.57 CH 2 ICOO~ + I*" H 2 10 3 A=3-7; 10 3B=8-17 NaOH 0.01-0.02 k AB 25 8.0 -4 (83>


60 1.49 -2 16 5 8

10 3A=4-7; 10 3B=7-15 -4 (83) CO


.58 CH 2 ICOOCH 3 + I*" H 30 feAB 0 5.8 K
25 7.5 -3 17 2 10

Halogen- subs ti tuted alkyl halide


CO
Na+ = B -3 ( 81)
.59 CH 2I Z + I*' C 2 5OH A=0.5; B=0.06 *AB 60 1.04

.60 CClgBr + BrBr* A B= 0.03-0.08 *AB 100 1.0 -6 * (38)


115 5. 1 -6 Oi
125 1.33 -5
135 3.3 -5 30
cci 4 A=0.-0.9; 1D 3 B= 3-8 135 2.8 -5
150 7.5 ~5
170 5.5 -4 29

Unsaturated alkenyl halide

Ll + = B -5 < 8r>
.61 CH 2 : CHCH 0C1 + Cl*" ( CH 3 ) 2CO 1___A^.l; B^0.03 k AB 44 5.87 *
Ll+ =B -5
(CH 3) 2CO + 30% CH 3N0 2 44 4.21

Na+ = B feA 14 5.0 -5 * (")


.62 CH 2:CHCH 2I + I*" C 2H 8OH A = B = 0.01
22 1.07 -4
28 2.2 -4
41 7.1 -4 17

National Bureau of Standards - National Research Council December, 1955


302.477
A = concentration of A + L and B = analytical concentration of B + M 1
k = A
Demasfineds i
t
1awacon Temperature k* x ion
Am o u n t of A x 10n Comments Literature
Amount of
No. React i on Sol vent Addend S
reactant addend
k n ,4 n

.63 CH 2:CHCH 2I + i g* C 6H 14 10 3 A = 7-300; (dark) feAB 0 7.7 -4 * ("x")


10 5B = 6-400 15 2.37 -3
5 6.0 -3
35 1.15 -2
40 1.74 -2 13. 1 2.5 7
CO
.64 CH 2:CHCH 2I + I* C 6H 14 10 3 A = 5-100 k AB 25 5 +6 * C 30 )

.65 CH g CH-'CHCH 2Cl + Cl*~ A^O.l; B^0.03 Li+ = B -4 ( 87)


(CH 3) 2 CO k AB 44 1.48 *

.66 + Cl*~ (CH 3) 2CO A^O.l; B^0.03 Ll + = B -6 ( 37)


GH A : CH(CHJCHC1
3 k AB 44 1.82 *

.67 CH g CH:CHCH 2Br + Br*~ (CH 3 ) 2CC A=0.1; B=0.04 Ll + = B -33 -4 <6)
k AB 3.49 *
-27 7. 13 -4
Oi
-19 1.98 -3 14.7 2 9

.68 CH:CH(CHjCHBr + Br*~ (CH 3 ) 2CO A=0.1; B=0.04 Ll+ = B - 6 -5 (8)


2 o k AB 3.44 *
16 3.67 -4
25 8.66 -4
30 1.42 -3 16.5 1. 1 9

.69 (CH 3 ) 2 GO A^O.l; B^O.03 Ll + = B -3 < 37>


(CH 3 ) C:CHCH 2 ci + ci*~ fcAB 44 1.25 *

Unsaturated alkynyl halides

.70 CHjccHgCi + ci** L1+ = B -5


(CH 3 ) 2CO A^O.l; B^0.03 k AB 44 6.57 *
< 37)
Unsaturated alkenyl Di-halides

.71 cis-or-trans-BrCHCHBr + Br 2* cci 4 -6 * ( 81)


A = 0.17; B = 0.01 k AB^ 30 7.5

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
3D2.477
A = concentration of A + L and B = analytical concentration of B + M
O) CO k = A =
c CO X o CO
ctJ rt A x I0n 3
S 3 k x 10n
"c * Amount of Amount of -H c -H
<D z C0 CD
Reaction So 1 vent Addend "0 C S L.
No. E ,_, o o 0>
to r eac tan t addend c Q-
io -H
-H k n A n o
M- O
0> Ctf 1 -J
1 * t

kAB* -5 <")
.71 cis-or^trons-BrCH^CHBr + Br g* cci 4 A = 0. 17; B = 0.01 36 1.50 *
45 4.4 -5 22 1 11
C continued^

-5 (24.)
.72 ci*-icH :cHi + i 2* decalin 10 3 A = 5-30; decalin feABi 76 1.2 *
10 3B =3-13 100 1.25 -4 25 4 9 CO

-4 ( 24 *)
.73 .2 trans-ICH'CHI * I g* decalin 10 3 A = &-30; feAB* 100 1.0 26 6 9 *
10 3B = 3-13
( 4)

C H A=0. 1; 10 6B= 3.5 25 8.3 -9 *


10 4B= 3.3 25 1.6 -8
10 6B= 3.5 H 2 trace 25 4 -8

( S6 )
.74 tran^-ICH^CHI + I* p 6nii !4 A=0.02-0.2; fe AB 25 2.6 +3 8 4 9 * Oi
10 LI J = 3. 5

Aryl-substi tuted alkyl hallde


Li^ -4 ("*>
Rr* 4-
PH jjDi
M .vXi RT ~
DI A=0.05; B=0.03 = B fc AB 6 1.21
.75 C n (CH 3COOCH 2) a
17 3.38 -4
25 7.89 -4
35 1.68 -3
45 3.64 -3 15.3 7 7

K+ -3 ( 32>
CACV + I*" CH 3OH 10 3A= 1-10; = B k AB 0 1.0 *
.76
10 3B= 1-10 27 1.5 -2
44 6.4 -2 16.2 1.0 10
10 3 A= 1-14; K+ = B 1.65 -4
CgH OH 0
10 4B= 8-130 27 2.87 -3
44 1.40 -2 17.3 1.2 11

Standards - National Research Council December, 1955


National Bureau of
Homogeneous Reaction Kinetics
302.477
A = concentration of A + L and B = analytical concentration of B + M 14
CO
CO 3 (D * = A =
(0 nJ CO
e k x \Q A* x ion 3
Amount of Amount of td C
No. T3 C (0
React 1 on So 1 vent Addend > 0
u S E
reactant C E
add en d .- *- Q. -M
**- 0
k n A n ^ ~
1
o m
0

.77 C 6H 5CH 2I + I 2* CC 1 2: ccicci:cci 2 10 4A = 1-1500; k AB* 60 2.15 -5 *


(8)
1D 5 B = 3-5000 -5
70 6.20
80 2.00 -4
90 5.41 -4 26.1 3 12

Ll+ CO
.78 -CH OC H CH Br + Br*~ (CH 3 COOCH 2) 2 A=0.05; B=0.03 = B ^AB -5 3. 14 -4 *
(34) K
3642 T3
5 8.33 -4 13
15 2.00 -3
25 4.52 -3 13.9 5 7

. sk L1+
.79 (CH 3 COOCH 2) 2 A=0.05; B = 0.03 = B te AB -7 2.29 -4 *
(3*>
5 9.47 -4
K*.
15 2.71 -3
CO
25 7.59 -3 16.8 1.0 10

.80 AnM* Li+ = B -3 I 1)


264 2
A=0.05; 10 4B = 1.2 feAB 0 8.98 *
6.0 0 8. 16 -3
21 0 5.62 -3
104 0 4.33 -3
380 0 1.98 -3
1.2 30 2.23 -1
4.9 30 1.60 -1
12 30 1.34 -1
102 3D 9.57 -2
313 30 7.5 -2
k i = k/a 0 1.01 -2
(a = calculated degree of dissociation of LiBr) 30 2.21 -1 16 1 11
LI"1" -5 -4
(CH g COOCH 2) a 10 2 A= 2-10; 1Q 2B = 1-10 = B feAB 4.57 *
(84)
0 7.56 -4
11 2.45 -3
30 5.41 -3 15.4 1.0 9

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
302.477
A = concentration of A + L and B = analytical concentration of B + M 15
CO b
K =
co s 0> c
0) Of (0
3 k x 10 A x I0 n -H 3
Amount of Amount of E -M C
o c <d O
No. React 1 on Sol vent Addend L. S E ?
reac tan t 0 E 0)
addend c OL 0
-H k A
>+- o E n n O
o> ^
h-
0

.81 MO.C.H.GH.I + i*- 10 4A= 5-30;10 4B= 4-30 K+ = B -3 ( 27)


CH o OH fcAB 0 2.2 *
30 1.5 -2
31 4.0 ^2 15.6 6 9
C gH BOH 0 6.0 -3
3D 5.0 -2 CO
31 1.32 -1 16.5 9 10

.82 4" (NOJ JLH -CH Br + Br*" LI* = B -27 -4 ( 34)


<c 6 4 t (CH 3 COOCH 2) a A= 0.05; B=0.03 fe AB 3.10 *
-3D 8. 16 -4
- 7 4. 3D -3 16.4 1.2 11

.83 CA A=0.03; 10 4B=6-70 *A 36 3.3 -5 ( 8B)


W.^^ieViW^ X * CO
50 7.9 -5
A/* A 5* Oi
^eV^oy^ - 017 50 1.3 -5
68 2.34 -4 12.4 -39
2J
k A + fc'AB 3 * 7
10 3 B > 7 50 k 1 -9.9 - +3
10 3B < 7 C 6H 5H ^ B k A + k "AX 50 k"= 1.05 -1
(X) |

Aryl halides
r
.84 CeV + : *~ -10 *
( I4,
CH 3c: N A = 0.74; B = 0.041 /? A 157 5.0
0.74 0.082 157 1.0 -9
0.33 0.164 157 2.8 -9
0.72 0.039 185 6. 1 -9
0.72 0.079 185 5.6 -9
0.32 0.158 185 6.9 -9
0.69 0.038 307 2.2 -8
0.69 0.076 307 3. 1 -8
0.31 0.153 307 2.4 -8

National Bureau of Standards- National Research Council December, 1955


Homogeneous Reaction Kinetics
302.477
A = concentration of A + L and B = analytical concentration of B + 16
w k = A
w * <D
eb cti Temper
ature k x ion A 10 n 1
Comments L_
Amount of E 3
Am o u n t of
No. Reacti on So 1 vent Addend "0 C S 5
9) 0 u
react ant addend C <D
* A
4- 0 n n
o? J _l
0

.84 CHI + I*" (continued) CH 3 C :"N A = 0.66J B = 0.037 kA 238 2.5 -7 * ( 14)
O o
0.66 0.074 238 3.0 -7
0.29 0.147 238 1.4 -7 24
Na+ = B -8 f 80 )
^C 8H 1? OH A = 0.02; B = 0.010 k A 240 1.9 *
-8 CO
0.020 240 1.7
0.040 240 1.4 -8
0. 10 240 1.6 -8

.85 p-EOC H -I + I*" Na+ = B -6 (")


6 4
2-C8 H 1?OH A = 0.02; B - 0.018 feA 192 4.6 *
0.01-0.02 0.01-0.1 200 7.5 -6
0.02 0.018 215 1.5 -5
0.02 0.02 231 4.2 -5
0.04 231 3.6 -5
0. 1 23J 3.4 -5

.86 o-N0 2C6H 4I + I*" CH 3 C|N A = 0. 18; B = 0.04 feAB 100 1.3 -6 * (")
0.16 0.09 100 7.2 -7
0.04 0.18 100 1 -7
0.04 0.16 157 6.4 -6
0.08 0.33 157 5.0 -6
0.16 0.04 157 2.0 -5
0.16 0.08 157 1.2 -5
0.33 0.08 157 3.4 -5
0.04 0.16 185 3.8 -5
0.16 0.04 185 8.3 -5
0.16 0.08 185 7. 1 -5
0.04 0.08 3D7 1.96 -4
0.04 0.15 207 1.8 -4
0.08-0. 15 0.04-0.08 207 2.5 -4

r
National Bureau of Standards - National Research Council December, 1955
Homogeneous Reaction Kinetics
303.477
A = concentration of A + L and B = analytical concentration of B + 17
CO A =
w s 4> k = o
l_ w l_
cd <o 3
s k x I0n A x lon 3
Amount of Amount of c +J
<ti <D cd
No. Reaction So 1 vent Addend o c L. * i_
<c o 0 E
c S <D
reactant addend Q- -H
s O
M- 0 k A O
0>
03 (0 t~ n n _J
O

.86 o-N0 2C 6H 4 I + I*~ (continued) CHC'N A = 0.04; B = 0. 15 k AB 238 8.9 -4 * (")


3 *
0.15 0.04 238 1.66 ~3 29

.87 m-NO C HI + I*~ CHgCJN A = 0.2-0.4; B = 0.04-C). 16 fc A 157 8 -9 * (")


O 4
185 3.6 -8
-7 CO
207 1.3 K
-7 13
238 9.4 25

.88 -9 ( 14)
^-N0 2C0H 4I + I*" CH.C'-N A = 0.04; B = 0.09 k AB 100 8 *
o
0.09 0.04 100 4.4 -7
0.04 0.08 157 1.4 -6
0.08 0.04 157 2.1 -6
0.04 0.08 185 9.7 -6
0.08 0.04 185 1.3 -5 Oi
-5 en
0.04 0.08 207 4.81
0.08 0.04 207 5.7 -5
0.2 0.04 202 5.0 -5
0.04 0.08 238 3.6 -4
0.07 0.04 238 5.0 -4 34
( 19 )
0.01-0.02 0,02 240 4.8 -4 *
0.02 0.06-0.12 240 3.8 -4
~" -4
a-c8H 1ToH feA 240 1.46

( 34 )
.89 2, 4, 6- (NO ) 0C H Br + Br*" (CH 3 COOCH S) a A = 0.05; B = 0.030 k AB -5 1.99 -4 *
3 o 2
0 3.92 -4
10 1.31 -3
22 4.53 -3 18.2 9 ID

(")
.90 HOOCCH(NH 2) CH 2-4r-HOC 6H 2-3, 5-1 + 1*- H 20 63 (no exchange In 2 weeks }

National Bureau of Standards - National Research Council


1 December, 1955
Homogeneous Reaction Kinetics
302.477
A = concentration of A + L and B = analytical concentration of B + M 18
A =
ion
Amount of Amountof
No. Reaction Solvent Addend
r eact an t ?Jdend

.91 HOOCCH(NH)CH-4-HOCH-3,5-I4-II -4 ( 39 )
22 62
1D 5A= 4-1500; CH 30 COOH A5ABLHT"
" SO 5.33
10 5B = 1-40 CH 3COONa -3
H 230 4 42 8. 11 -3 23 13
NaHS0
Co

SOLVENTS

AnM (CHJ-CO + 5 vol % CH OH

COMMENTS

General. The halogens marked X* are radioactive isotopes. was not introduced to its concentration at infinite time in
Pseudo first order exchange rates are observed, and isotope that same species. The exchange rate R= f(a, b, catalyst)
effect, (appreciable difference between rate constants for such as k AB, k AB^ or more complex expressions. For a more
forward and reverse reaction) is considered negligible. The complete treatment see ( 9a)( 21a). Rates of exchanges in-
kinetic rate law and the chemical reaction rate constant volvinghalogen salts Innonaqueous media in general parallel
are calculated from the dependence of the exchange rate, apparent degree of lonlzation from conductivity data. For
P ""50 ''Jfib
R= (a+b) t "log( 1-%/xJ , upon the concentrations of A+L and this reason the reacting species Is listed as the halogen
B+tt and any catalysts, where a is the stationary concentra- Ion, but the rate constants and concentrations are in terms
tion A+L, b Is the stationary concentration B-m, and %! *& of the total analytical, ionized and unionized salt concen-
1s the measured ratio (at time t) of the concentration of tratlon.
Reaction. (.20) (.22) Values of rate constants at concen-
the labeled Isotope in the molecular species in which it

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
302.477
19

COMMENTS (continued)

tratlon, (b), other than 0.024 M/l converted to this con Tables. (.29) Values of rate constants by ( 28 ) cor
centration by the empirical relation rected from erroneous values In 1951 Edition of Tables.
10g(/ebA0>024) = -0.37 10g(b/0.024). Negative salt effect. Selected data of ( 21). ( 4) converted
( 3) found this transformation valid for each alkyl bromide rate constants to same concentrations of Nal by empirical
studied over a temperature range from 26 to 65C and for equation, see (.20) (.22). (.30) Authors showed ob
lD 3b = 1.6 to 100. (.23) Values of rate constants by served rate law to be consistent with mechanism involving
C 28 ) corrected from erroneous values In 1951 Edition of fairly stable complex between reactants with^ as the equili
CO
Tables. Selected values listed from ( 7 ) ( 8 ). Negative salt brium constant for the dissociation of this complex.
effect observed by ( 4) who converted values of rate constants (.31) Selected data. (.32) Negative salt effect.
CO
to the same concentration Nal by empirical equation, see Values of rate constants converted to the same concentra 3
CO
(.30) (.22). (.24) Converted to sec. from original mln. tion of LiBr by empirical equation, see (.SO) (.22).
(.26) Negative salt effect observed by ( 3) who converted (.33) Negative salt effect in acetone with LiBr. ( 3) con
values of rate constants to the same concentration of LIBr verted values of rate constants to same concentration of CO
Oi
by empirical equation, see (.20) (.22). (.27) Negative LiBr by empirical equation, see (.20) (.22). ( 15) obtained
salt effect. Rate constants converted by ( 3 ) to the same straight line In plot of exchange rate divided by (A+L), R/(A+L),
concentration of LIBr by empirical equation, see (.20) (.22). versus a(B+M) where aisthe degree of dissociation of LiBr
( 15) obtained straight line In plot of exchange rate divided from conductivity measurements. The intercept and slope gave
by (A+L), R/U+L), versus a(B+M) where a Is the degree of k andfc respectively. A small positive salt effect observed
dissociation of LIBr from conductivity measurements. Negli by ( 5) InCHgNOgWith (C 2H s) 4NBr the halide salt. (.34)
gible Intercept may be taken to Indicate the low reactivity of Selected data of ( X1) and ( 21). ( ll) proposed results to
undissociated salt. (.28) Values of rate constants by indicate that l" is the reacting species for the alkali
( 28 ) corrected from erroneous values in 1951 Edition of halides, the undissociated molecule or a complex ion in the

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
____ 302.477

COMMENTS (continued)

case of Znl g and an associated complex such as CdCdl 4 in at 25C extrapolated from measured values probably between
the case of CdI 2 which showed third order behavior on the 30 and 70C. (.51) (.52) Rate of deuterium exchange
basis of a single variation in concentration of Cdl by a between DC1 and camphene hydrochlorlde about 30% faster than
factor of only two. Units of ( ll) converted to sec. from halogen exchange, see 302.401. (.53) Rate constant at
original hours. (.35) Reacting species in all solvents 25C extrapolated from measured values probably between 30
studied considered to be I" andnotHI, however in n-hexanol, and 70C. (.60) Units converted to sec. from original
n-dodecanol and acetic acid authors consider simultaneous hrs. (.61) Units converted to sec. from original mln.
to
reactions involving I" and HI ~ contribute to rate. By es- (62) Units not stated and calculations not illustrated,
2
timating degree of dissociation of HI and of formation of HI" assumed base e logarithms and sec. from calculations from
from conductivity data values of the reaction rate constants illustrative curve. (.63) One hundred fifty fold
CO
for each reacting species were estimated. Units converted variation in B+ft shows only first order rate with respect to
to sec. from original hrs. (.37) (.38) Selected data. I g thus Indicating molecular I g rather than atoms to be the
(.39) Negative salt effect. ( 4) converted rate constants reacting species. Addition of small amount of water caused
to same concentration of Nal by empirical equation, see no effect. Slight inhibition by 0 2 from air as 12$ increase
(.SO) (.22). Corrected for parallel reaction believed to be in rate observed on sweeping N . (.64) Units
eliminatlonwitholefin formation. (.40) (.43) Negative converted to M/l fromM/ml. I atoms produced photochemlcally
salt effect. Rate constants were converted to same concen and accuracy limited by estimation of concentration of atoms.
tration of alkali halide by empirical equation, see (.30) (.65) (.66) Units converted to sec. from original min.
(.22). (.44) E converted from original E' of ( 34) by (.67) (.68) Negative salt effect. Values converted to same
adding RT. (.45) Rate constant at 2x5 extrapolated concentration of LiBr. (.69) (.70) Units converted to
from measured values probably between 30 and 70 C. sec. from original min. (.71) No difference observed
(.46) Selected data. (.47) (.49) (.50) Rate constants in exchange rate for cis- and trons-isomers. Units converted

National Bureau of Standards - National Research Gourci \ December, 1955


Homogeneous Reaction Kinetics
302.477

COMMENTS (continued!

to M/l fromM/ml. (.72) Values corrected from erroneous peratures. Addition of free I 2 accelerated rate 10 to 15%.
values In 1951 Edition of Tables. Units converted to M/l Addition of 0.5 9ns. H gO orNa S0 3 retarded rate about 15%.
from original M/ml. (.73) Units converted to sec. from Selected data. (.85) No calculations shown, or units
hrs. (.74) Iodine atoms produced photo chemically and which were assumed to be hrs. and converted to sec.
CO
accuracy dependent upon the determination of the concentra (.86) Free I_<j formed after about 30% exchange. i n made no
tion of atoms. Units converted to M/l from original M/ml. noticeable effect on exchange rate. Units converted to sec.
(.76) units converted to sec. from original min. (.77) from original hrs. (.87) Units converted to sec. from
Reaction inhibited by oxygen. Considered to involve chain original hrs. First order rate constants erratic but show
mechanism and rate constants for the seven individual steps less deviation than calculated second order constants.
calculated by authors. (.78) (.79) E converted from E 1 Appreciable free I and black precipitate formed at 238C.
CO
of authors by adding RT. (.80) In ethylene glycol (.88) Units of ( 14) converted to sec. from original hrs. Oi
Ol
diacetate E converted from E1 of ( 34) by adding ^RT. Units of ( 10 ) converted to M/l from original mM/1. First
(.81) Units converted to sec. from original min. (.82) order rate constants showed less variation than calculated
E converted from E 1 of ( 34) by adding RT. (.84) First second order constants in 2-octanol. Second order rate con
order constants erratic but show better agreement than cal stants showed less variation than calculated first order
culated second order constants. Units converted to sec. from constants in acetonitrile. Method of calculation not indi
original hrs. Units and calculations not shown by ( 20 ) but cated by ( 19 ). (.89) E converted from E' of ( 34) by
assumed to be hrs. from comparison with values by ( 14). adding RT. (.91) No exchange observed in 34 hr. period
( 14) observed formation of black precipitate at higher tem at 52C with CH 3OH or C AH OOH as solvent.

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics

______302.477 _____________________________________ ___ _________________________22

LITERATURE
(*) &D. Bowers, J.M. Sturtevant, ACS 1955, 77, 4903. ( 2) P. B. D. de la Mare, CSL 1955, 3169. ( 3) P. B. D.

de la Mare, CSL 1955, 3180. ( 4) P.B.D. delaMare, CSL 1955, 3196. ( 5) P. B. D. de la Mare, E. D. Hughes, C.K. Ingold,

Y. Pocker, CSL 1954, 2930. (8) B. D. England, CSL 1955, 1615. ( 7) C. C. Evans, S. Sugden, CSL 1949, 270.

(8) C. C. Evans, S. Sugden, J. Chin. Phys. 1948, 45, 147. ( 9) M. Gazleth, R.M. Noyes, A OS 1955, 77, 6091. ( 9a) G.M.

Harris, TFS 1951, 47, 716. ( 10 ) R. D. Heyding, C. A. WlnfcLer, CJC 1951, 29, 790.

( n) G.W. Hodgen, H. G. V. Evans, C. A. Wlnkler, CJC 1951, 29, 60. ( la) J. H. Hodges, A. S. Mlceli, J.C.P. 1941, 9, 725.

( 13) R. A. Howald, J.E. Willard, ACS 1956, 78, 6218. ( 14) A.M. Krlstjanson, C. A. Wlnkler, CJC 1951, 29, 154.

( 15) L.J. LeRoux, E. R. Swart, CSL 1955, 1475. ( 16 ) S. May, P. Daudel, J. Schottey, M. Sarrof, A* Vobaure, OR A 1951,

232, 727. ( 17 ) S. May, A. Fava, B. Giraudel, OR A 1953, 236, 286. ( 18 ) S. May, B. Glraudel, CRA 1952, 234, 326.

( ie) S. May, B. Giraudel, CRA 1952, 234, 2280. (*) S. May, M. Sarrof, A. Vobaure, P. Daudel, CRA 1951, 233, 744.

^
( 21) H.A.C. McKay, ACS 1943, 65, 702. ( 21a) H. A. C. McKay, SAT 1938, 142, 997. ( 22) V. B. Miller, M. B. Nelman,

Yu. M. Shapovalov, DAM 1950, 75, 419. ( 23) T.P. Nevell, E. DeSalas, C.L. Wilson, CSL 1939, 1188. ( 24) R.M. Noyes,

ACS 1948, 70, 2614. ( 24a) R.M. Noyes, R. G. Dlckinson, V. Schomaker, ACS 1945, 67, 1319. ( 2C) R.M. Noyes, D.J.

Slbbett, ACS 1953, 75, 767. ( 2e ) R.M. Noyes, J. Zlmmerman, J.C.P. 1950, 18, 656. ( 27 ) E.L. Purlee, M. Kahn,

J.L. Riebsomer, ACS 1954, 76, 3796. ( 28 ) H. Seelig, D. E. Hull, ACS 1942, 64, 940. ( 29 ) D.J. Slbbett, R. M. Noyes,

ACS 1953, 75, 761. (*) D.J. Sibbett, R.M. Noyes, ACS 1953, 75, 763.

National Bureau of Standards- National Research Council December, 1955


Homogeneous Reaction Kinetics
___ 302.477 23

LITERATURE (continued) Co

( 31) H. Stelnmetz, R.M. Noyes, ACS 1952,74,4141. ( 32) P. Stillson, M. Kann, ACS 1953,75,3579. ( 33) H. V. D.
CC)

Straaten, A,H.W. Aten, ACS 1954, 78, 3798. ( 34) S. Sugden, J. B. Wlllls, CSL 1951, 1360. ( 35) C. G. Swain, M.M.

Kreevoy, ACS 1955, 77, 1182. ( 3Q ) & F. Van Straten, R-V.V. Nlcholls, C. A. Wlnkler, CJC 1951, 29, 372. ( 37 ) C. A.

Vernon, CSL 1954, 4462. ( 38 ) J. Wlllard, A. Miller, J.C.P. 1949, 17, 168. ( 39 ) A.H. Zeltman, M. Kahn, ACS 1954,
Oi
76, 1554. ( 40 ) J. Zlmmerman, R.M. Noyes, J.C.P. 1950, 18, 658. Oi

National Bureau of Standards- National Research Council December, 1955


Homogeneous Reactions ISOTOPE EXCHANGE Liquid phase
302.506 Hydrogen Isotope between Vth Group Element and Oxygen Amounts are in M/ I.
Rate const ants are in
M/ I and sec.

0
k -
i_ o O
1~
3 k x ion +>a
c ^ H 3
Am o u n t of Amount of Def i ned mass c 4->
o 3 d -H
> '-5 L. 0 Of
No. R e ac t i o n Addend 1
4- E
O
J s r eactan t addend act! on 1 aw Q. "5 E *-e
E k n
4>

x s _j
CO

-) f 1)
.1 NH.NO, + DN0 0 >NH 0DNO, + HN0 J0 H 20 B = 11.6 0 60-60(
4 o o 3 3
t?d
/ 2\
.2 NH NO. + TO0 0 >NH fl TOO, + HNO, H 2 B = 11.6 0 180
4 o o o 3 O

.3 D+ + CH OH
+ + CH (3D >NH 33
NH 43 HC'ON (CH g) 2 A= 0.3-0. 5; HBr 0.001-0.1 feABtHT 1 0 2.5 -5 * ( 3)
_^^_^_
B = 0. 1
0.06 CD
B A = 0. 1 HC1 rel. rate 1 01
01

.4 C 2H 0NH 3'f + CH 3 D ""~* C 2H 5NH 2 D+ + CH 3H B A = 0.1 HC1 0.06 0 0.07 * ( 8)


/ 3\
.5 0H_) NHD+ + CH.OH B A = 0. 1 HC1 0.06 0 0.10 *
3
(C H ) NH + + CH OD > (C 252
2522 3

B A= 0.1 HC1 0.06 0 0.5 * ( 3)


.6 (CH J NH* + CH 0OD > (CH oJ oW + CH o OH
33 o

CHCl g A= B = 0.1 0 120 ( 2)


.7 (CH g) 3NH+ -f C4H9OT > (CH 3 ) gNT+ + C^OH cr
B A = 0.1 HC1 0.06 0 9 * ( 3)
.8 (C H ) NH+ -f CH OD > (C H ) ND+ + CH OH
253 3 253 3

\Tti"^" j_ n f\T MT 4- f R HW A- B = 0.1 0 3 6 x 104 ( 2)


.9 (C TT 5'\ 3^
/ p 2H U 9
C4H T ^ (( P U 5 \) 3NT
SH C4HQH CHCl g cr
B A = 0. 1 HC1 0.06 0 >100 *
.10 C6H 5NH 3+ * CH 3 D ^ C6H 5NH 2D"h * H 3 H

National Bureau of Standards - National Research Counci I December, 1955


Homogeneous Reaction Kinetics
302.506

0) k =
3 (O i-
I 7 Amount of -M fe x ion M 3
No. Amount of Defined mass c
Reaction ~ XJ Addend o of
1
o ^ reactant E u.
addend action law Q. E 0>
i X
* n O
I- -
.11 PH 3 + HOD 5>PH 2D + H gO TT f\
B A = sat. at O + buffering fcAX 27 3.6 0 *
(4)
100-500 mm. HCOOH salt feAX 27 2.1 -3
CHgCOOH fcAX 27 9.4 -4
(CHJ-CCOOH feAX 27 4.7 -4
OH 1 /SAX 27 4.0 -1
Co
COMMENTS
CC)
Reactions: (.3) Rate constant calculated using rate law given by authors and half-time for exchange given at only one
CO
point. Exchange rate Independent of which compound was labeled. This reaction used as reference for relative
rates of alkyl ts.
substituted ammonium ions in me than ol. No actual rates given. (.4) (.5) (.6) Relative rate with reference to (.3) as
unity. (.8) Relative rate with reference to (.3) as unity. Negative salt effect observed with 30 % decrease in rate K*

Oi
constant in methanol on going from 0.05 to 0.4 M/l Initial concentration of A. Increasing polarity of solvent
observed to
usually decrease rate of exchange. Reaction immeasurably fast in toluene with rates in C 2H OH faster
than in CH OH and
si o win ethyl ene glycol. In organic acids as solvents, HCOOH or CHgCOOH, rate of exchange immeasurably fast.
(.10) Rate
relative to (.3) as unity. (.11) Reaction carried out in two phase system, gas and liquid, and rate constants cor
rected for amount of A in gas phase as exchange Is limited to liquid phase. Conditions such that diffusion
between phases
was at least ten times faster than the reaction studied. General acid and base catalysis observed and rate
of exchange is
2fe1 A[catalyst] 1. Catalyst constants for the acids were corrected for oxoniura ion catalysis but no
correction made for
catalysis by conjugate base in buffer solution, (acid and conjugate base always equal.) Slight positive salt
effect observed
with NaCl at constant pH using benzole acid, sodium benzoate buffer. Over temperature range 27-50C activation
energy for
both H O4" and OH~ catalysis is 17.6 Kcals. Preexponential term being 2.4 x io 13 and 2.7 x 10 12 respectivel
3 y.

National Bureau, of Standards - National Research Counci I


December, 1955
Homogeneous Reaction Kinetics
302.506

LITERATURE

(*) A. I. Brodskll, L.V. Sulima, Doklady Akad. Nauk. SSSR, 1950, 74, 513. ( 2) L. Kaplan, K. E. Wllzbach, ACS
4
1954, 76, 2593. ( 3) C. G. Swain, J. T. McKnlght, M.M. Labes, V.P. Krelter, ACS 1954, 76, 4243. ( ) R.E. Weston,

J. Blgelelsen, ACS 1954, 76, 3074; R. E. Weston, J. Blgelelsen, J.C.P. 195a 20> 1400.

National Bureau of Standards- National Research Council December, 1955


Homogeneous Reaction! ISOTOPIC EXCHANGE Liquid phase
302. SOB H - D exchange on N in VI Nth Group Complex Amounts are in M/ I.
Rate constants are in
M/l and sec.

0) k =
to f o
ratur
Tempe Comments
i 1 Amount of ma
ned
Def
i actlaion
No. Reaction T> > Addend PH S
o reaotan t
5 CO
f n
SD P LEM E1
.1 Co(ND )+ + "*'+ 18H 00 >Co(NH_) A f + + -f- 18HOD B 10 3A= 6-60 Na2HP0 4, KH 2P0 4 4.7-5.6 * A[H+]~ I = 20 4. 14 -9 *
o O 2 o o
10*A = 4.8 4.81 -dA/dt 0 1.18 -10
8 5.55 -10 %
15 1.95 -9
22 6.06 -9 28.4 M
CD
01
.2 B 10 2A =3-14 Na2HP0 4 , KH 2P0 4 4.4r-4.8 0 2.46 -10 * 01
-dA/dt 8 9.7 -10
CoOfHgO^CHgKHg) *"*"*" + 12HOD
15 3.38 -9
22 1.05 -8 28.1

COMMENTS
Reaction. (.1) Pseudo first order exchange rate constant Independent of concentration of A or fraction of heavy isotope
in A- Observed pseudo first order constant inversely proportional to corrected hydrogen ion activity. pHof buffer dependent
upon concentration of trlvalent cobaltic ion. If this correction Is not made exchange rate appears to be dependent upon
A~* 54 power. Addition of KClorNfcLNO

a3 had no effect on rate constant. (.2) Rate constant calculated by multiplying
observed pseudo first order exchange rate constant by corrected hydrogen ion activity. Observed pHof buffer corrected for
Influence of triply charged cobaltic ion.
LITERATURE
J. S. Anderson, H.V. A, Briscoe, N.L. Spoor, CSL 1943, 36JL

National Bureau of Standards - National Research Council December, 1955


X
a
0
^
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0 **
O
10
^ ^ ^
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CO
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-* P
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0 0
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1 ? D3 uB action 1 aw
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CD CD 8 g
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<i to
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. (ft
* * Comments
QS6T
Hornoffinaoui Rtact ions EXCHANGE Gas phase
311.417 Halogen replaced by H on aliphatic C
Reaction type: RX + HX RH + x.2 Amounts are in M/1.
(A) (B) (L) (M) Rate constants are in
M/i and sec.
Rate measured: dM/dt

0> k = ,4 = o
L. 01 w.
3 k x jon A x ion -H
-H 3
Defined mass <tf c -H
l_ 0 Of
No. R e ac t i o n Amount of reactant I S E L.
O 4) CO
D. E
action 1 aw -H
k ^ n 3 a

-
n 1

CK)
PW > ptl -3 * (')
.1 ni '"^^
on aiT -4-* UT ^*"A J. T o 10 A ~ 2~8j 10 B ^ 3 k AB + k AB/B 270 8.0
280 1.5 -2
290 2.5 -2
300 4.4 -2
-2 CO
310 7.2 01
320 1.14 -1 33.4 2.3 11 01

270 2.7 -5
280 5.2 -5
290 1.03 -4
300 2.00 -4
310 3.58 -4
320 7.0 -4 43.0 3.9 12
10 3A = 2.3; 10 3B =1.3 320 5.2 -4
0.4 0.8 320 5.7 -4
0.9 0.4 320 3.6 -4
0.3 0.2 320 2.4 -4

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
311.417
d> k = A =
U 0
3 w
-M
h x ion ,4 x I0n *- 3
Defined mass (0 C -H
No. Reaction Amount of re act ant k. <u Of
0) t_
ac t i on 1 aw Q. 8 0>
O *-"
1 C3
h-
k 0 n ^0 n _J

.2 C I+HI-H>CH +1 10 3 A= 1.1-2.5; 10 3B=4.2-5.0 k AB + k AB/B 250 2. 18 -2 *


(*)
260 3.70 -2
280 1.02 -1
290 1.65 -1
300 2.63 -1 29.8 6.3 10
Co
k2
250 2.50 -5
260 5.5 -5
CO
280 2.34 -4
290 4.7 -4
300 9.2 -4 43.0 1.8 13
i0 3A = 0*45; 10 3B =1,1 300 9.1 -4
1.0 0.45 300 7.7 -4
0.12 0.34 300 6.6 -4
0.11 0.25 300 6.1 -4
0.13 0.20 300 5.7 -4
0.22 0.14 300 5.6 -4
0. 13 0. 17 300 4.5 -4

.3 n tj IT Ti try
/"i^n J0 3A ~ 1; 10 3B ~ 5 k AB+ k AB/B 260 1.67 -2 *
( 2)
O Y
"RO 4- T1 oi
Hi 5> nHIJ H
270 2.84 -2
280 4.7 -2
290 7.6 -2
300 1.14 -1 29.2 1.6 10
k2
260 8,3 -5
270 1.83 -4
280 3.7 -4
290 7.5 -4
300 1.40 -3 43.0 2.8 13

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
311.417

* k = A = 0
</>
3 A x 30 3
Defined mass k x ion c -H
No. React? on a) <D 0)
Amount of reactant K &
act! on 1 aw E O
a. O
e fe n A n O <::
i-

.4 Cl 3 CBr + HBr > Cl gCH + Br g 10 2A - 1. 1-2.5; 10 3B = 0.&-39; feAM^/(l + KM/B) 147 -5 (3)
3.64 24.5 *
10^1 = 1.7-4. 1 169 2.55 -4 24.8
182 7.57 -4 25.5 32.9 5 12

.4.1 JD'A -!;. ^=1.7-4.! k AB 147-182 10.2 8.1 10 *


Cl 3 CBr + Br 5> ci C* + Br (3)
33

Rf*
or '' *^
^ VJL
PI Oun
rH-J ^^ Rr
-4- DC i\
{/ I; ^AB, -120 k/k n = 1.4 1 *
(1) CO
1' 2
.4.2 ( 3)
k AB 147 4. 1 0 "2*
r g >Cl 3CBr -*- Br (2)
t 169 4.0 0
182 3.9 0 CO
CO

COMMENTS
Reaction. (.1) (.2) (.3)
Reaction followed spectrophotometrically and homogeneity proved by packing. Values tabulated In CO

original article in error by factor of ten which is corrected here. Pseudo second order rate law followed throughout 70% Oi

of the course. Values of k and k calculated from pseudo second order constants to include dependence of rate upon initial
concentration of B. In all cases feg, the calculated first order constant, was found to fall off at lower pressures although
It was reproducible and constant at higier pressures. (.4) Occurs simultaneously with reverse reaction, see 311.471.
Thermal reaction in dark with equilibrium Br ^ SBr followed by 4.1 as rate controlling step in long chain
k ^3
C1 3O + HBr -^ClgCH + Br and Cl gC- + Br 2 ^ClgCBr + Br.
K = k 9/h 2 also determined by Independent kinetic study. Value of K determined by ( s) does not agree with value of ~7
calculated by ( x) from photo bromlnation of C1 3CH at 110 to 130C. Homogeneity proved by Increasing S/V ratio six fold with

National Bureau of Standards - National Research Council


December, 1955
Homogeneous Reaction Kinetics
311.417

COMMENTS (continued)

no effect on reaction rate, (.4.1) Rate controlling step In (.4) as well as in radioactive exchange, see 301.477.
(.4.2) Competing reactions for Intermediate produced in rate controlling step.

CO

LITERATURE
Cn
Ol
(*) V.V. Braunworth, H.J. Schumacher, Kolloid Z. 1939, 89, 184. ( 2) R. L
Ogg, ACS 1934, 56, 526. ( 8) J. H. Sullivan, N. Davidson, JCP 1951, 19, 143.

National Bureau of Standards - National Research Council December, 1955


SUPPLEMENT 1955
ur>
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ON

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X
Homogeneous Reaction Kinetics
311.471
k -
1
Temp
ratu
re ion 1
Comments
Amount of Amount o1 A x ion eratu
t
i
Lre
Addend Def i ned mass
No. React ion K S
reactant addend act i on 1 aw
n n

.4 10 3A= 5-14;
(CH)
94
C + Br A > (CH J CCH Br + HBr fcAB*(t=0) 197 6.3 -2 *
(") (")
332
10 4B=5-14
.4. 1 J C + Br > (CH ) CCH -f HBr
(CH 34- (From .4 and phot o chemical reaction) AB 197 3.6 +5 18 9 13 *
( 6) (8)
332

(HBr > (CHJ C -f Br (i) (From .4 and phot ochemlcal reaction) k AB V*2 ~1D -6 (6) (8)
.4.2 (CH ) CCH + 1 3 4
33 2 Br > (CH) CCH Br + Br (2)
t 2 332

.5 C6 H 5CH 3 + Br2 >C6H 5 CH 2Br + HBr 10 3 A=4-'7; k AB^ ( t=0) 166 2.9 -3 ( 2)( 10 )
*
10 4B-4-10 2 0.0003 166 7 -4

.5.1 CH CH 0 + Br > C H CH + HBr 8.7 +6 7.6 ( 2) ( 10 )


653 652
(From .5 and photochemical reaction) k AB 166 6 10

( 2)( 10 )
HBr >C 6flH 5KCH 3Q + Br (i) (From . 5 and phot ocheralcal reaction) k AB k/k 5 1 3
.5.2
B > c H CH g r + Br (2)
{ 2 652

.6 Br + HBr 10 3A=6-10; K AB^ ( t=0) 5.1 -3 (7)


CH 3 Br + Br 2 ^ CH 22 297 *
10 4B=7-15

.6.1 CHgBr + Br >BrCH 2- * HBr 16 9 (7)


(From .6 and photochemical reaction) k AB ^330 2

.7 Cl CH 4- Br >C1 CBr + HBr 10 2A= 1.4-4; (*)


323
M 0-0.037 fcAB*/(H-KM/B) 147 3.01 -6 0.040 3 *
10 4B=2-38 169 2.01 -5 0.0403
( 9 ) (*)
182 5.78 -5 0.0392 32.0 1.4 11

.7. 1 C1CH + Br >C1 C- + HBr (From .7 and phot ochemlcal reaction) k AB 147- 182 9.3 2.3 9
3 3

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
311.471
k = *=
ID A x i
Am o u n t of Amount of Defined mass
No. Reaction
re act ant addend action law

HBr C1CH ( i) (From .7 and photochemical reaction) kj 147 4.08 -2 (9)


3 + Br
169 4.03 -2
Br
182 3.92 -2

Co

COMMENTS

General. Both thermal and photo chemical reactions studied, Inhibition by HBr observed in all photochemical studies and
but only thermal rate constants tabulated here. Halogenation ratio of rate constants for reactions (4) and (3) determined
assumed to proceed by the same mechanism as that forH + Br 2~~^ by varying initial concentration of HBr. Effectiveness of
<>
see 311.700, with photochemical reaction differing from A as third body in recombination reaction (5) varies from CJT
thermal reaction only in initiating step of the chain: a relative value of one for H g to 174 for neopentane.
Photochemical, Reaction. (.1) Only initial (extrapolated to zero time)
(1) Br 2 + h& >2Br and thermal, rate as reaction followed by (.6) which is almost ten times
(la) Br 2 + X * 2Br + X faster. Inhibition byM studied only for photochemical reac
(2) Br + RH >R- + HBr tion. Mechanism Indicates A to be 1.6 times more effective
(3) R. + Br 2 >RBr + Br than H A for recombination of Br atoms. (.3) Only
(4) R- + HBr >RH + Br initial rate (extrapolated to zero time.) Inhibition by M
(5) 2Br + X >Br g + X. studied for both photochemical and thermal reaction with
This leads the thermal rate being given by values of K disagree ing by 80$. It is possible that another
-dB/dt = competing reaction for (CH ) 3 O such as (CH 3) O >
1 +

National Bureau of Standards- National Research Council December, 1955


Homogeneous Reaction Kinetics
311.471

COMMENTS (continued)

CH 3 + CHCH-'CH
J
should have been included in the reaction finned. (.5)
Only initial rate, extrapolated to zero
mechanism. Inhibition by oxygen demonstrated. (.3.2) time. Inhibition by oxygen shown and inhibition by M demon
Variation in ratio of fc/^ by 30$ depending upon whether strated for the photochemical reaction. (.6) Only
thermal or photochemical reaction measured. (.4) Only Initial rate, extrapolated to zero time, although no appre
initial rate f extrapolated to zero time as rate of further
ciable inhibition by M observed and subsequent bromination
bromination of L not known. Inhibition by M and 0 demon
appeared slow. Mechanism indicates A to be 1.2 times more
strated for the photochemical reaction. Reaction mechanism
effective than hydrogen for recombination of Br atoms. Co
indicates A to be 174 times more effective than H for re-
2 (.7) Forward and reverse reaction simultaneously as well
combination of Br atoms. (.4.1) Reaction mechanism
(X)
as Independently studied. See 311.417. Homogeneity proved
of ( 6) ( 8 ) didnot Include competing reaction (CH) QCCH- >
33 2 by increasing S/V ratio by factor of 6. (.7.2) Ratio
CH-
9
+ (CH) o Jt>
C'CH. Inclusion of this would reduce E to
of fcjAo of ( 9 ) about one third the value reported by ( 4)
~12 Kcals. and give normal steric factor according to ( 3). at ~130C but ( 9 ) studied both forward and reverse of reac
Product analysis not performed so this has not been con- tion (.7). CO
Oi

LITERATURE
(*) H. C. Andersen, E.R. Van Artsdalen, JCP 1944, 12, 479. ( 2) H. R. Anderson, H. A. Scheraga, E. R. Van Artsdalen,
JCP 1953, 21, 1258. ( 3) S. W. Benson, H. Graff, JCP 1952, 20, 1182. ( 4) V. V. Braunworth, H.J. Schumacher, Kolloid Z.
1939, 89, 184. ( 6) B. H. Ecfcstein, H. A. Scheraga, E. R. Van Artsdalen, JCP 1954, 22, 28. ( 6) E.I. Hormats,
E.R. Van Artsdalen, JCP 1951, 19, 778. (7) G. B. Klstlakowsfci, E. R. Van Artsdalen, JCP 1944, 12, 469. (8) F. E.
Schweitzer, E.R. Van Artsdalen, JCP 1951, 19, 1028. (9) J.H. Sullivan, N. Davldson, JCP 1951, 19, 143. ( 10 ) E. H.
Swegler, H. A. Scheraga, E.R* Van Artsdalen, JCP 1951, 19, 135.

National Bureau of Standards - National Research Council


December, 1955
SUPPLEMENT 1953

- 02

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Homogeneous Reaction Kinetics
311.540

COMMENTS ( continued)

at 625C, lowers the rate by a factor of ~0.9. In pyrex at 550C the rate is about 50^ higher than in silica.
Surface in crease by a factor of 4 increased the rate (in the aged walls) by about 30^ at ^600Cbut has no appreciable
effect at 650-675C.

CO
K
LITERATURE 1
(fc
a N. Robertsan, R. N. Pease, ACS 1942, 64, 1310

CO
Ot
CO

National Bureau of Standards- National Research Council


December, 1953
Homo gtnioui Rotetions EXCHANGE Liquid phase
312.421 H on Al iphatic C with llnd group metal Amounts are in M/l.
Rate const ant s are i n
M/l and sec.

> k =
H- *
0 -a (0
3 k x lon -
-M 3
Amount of -H c Defined mass c
No. Reacti on Sol vent Addend
A#* Aj* ed
s
0) E u
r e ac t an t acti on 1 aw O
Q. CO
I 1 fe
n 0 C3
t- -J

.1 CHCOOH 4- Hg"*4" > (products not determined) CHgCOOH B = 0.095 -dB/dt = feB 50 9.5 -8 *
t 1)
3
70 1.03 -6
90 8.0 -6

Metal replaced by H on aliphatic C CO


Ol
-5 (2) 01
^^C.H + CH,COOHgC AHQ CH-COOH 10 2 A = &-6 feA 50 3.76 *
.2 H) Hg + CH^COOH 4 1U o 4 w 0
3
(n-C 492
75 3.91 -4 ao -16

CH 0 OOOH 10 2A = 5-6 feA 25 2.30 -5 *


(2)
.3 [C 2H B (CH 3 )CH] gHg 4- CHgCOOH > o
50 1.47 -4
n~ C AH in + CH 0 COOHgCH(CH J C H
* *u 3 3*5

10 2A^9 feA 75 1.02 -5 *


(2)
.4 [C6H 6C(CH 3 ) gCHg] 2Hg -H CH 3COOH > CHgCOOH
0.05 75 9.5 -6
5 CHgCOONa
C 6H 5C(CH 3) 3 4- CH 3COOHgCH 2C(CH 3) 2C 6H 6 -5 -17
5-6 0.0 100 9.35 23
0.022 k A[HC10 4] 50 7.0 -3
6 HC10 4
0.045 50 6.7 -3
3

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
312.421

COMMENTS

Reaction: (.1) Appears to involve formation of one C-Hg bond per Kg4"* reacting. Studied in order to correct for this
simultaneous reaction to aromatic mercuratlons in CH.COOH.
3
See 312.412. (.2) (.3) (.4) Rate law followed up to 85%
reaction. Second alkyl mercury bond remaining after ID to 20 half lives for first bond replacement, in presence of HC10 4
oxidation of solvent leads to Increase in acidity and separation of metallic mercury after 40-50% reaction.
CO

CO

LITERATURE
H, C. Brown, C. W. McGary, ACS 1955, 77, 2306. ( 2) S. Winsteln, T. G. Traylor, ACS 1955, 77, 3747.

National Bureau of Standards - National Research Council December, 1955


Homoginioui Huctloni EXCHANGE Liquid phase
312.422 H of Aromatic compound with Group II metal
ArH + M"1"*" ' Amounts are in M/ I.
Reaction types:
Rate constants are in
ArH + RM ArM + RH M/1 and sec.

Ar M + AcH - ArH + ArMAc

CO k = A =
CO X O
L_ (0 L.
(0E (If
3 K
b *>
y 1U
1H^ j4 x K)n H
E "t^
C ^
3 Amount of Amount of rt <D
"O C i
*^ Addend 0 0 E U
No. Reacti on 0 E <D CO
addend c Q. 4J
* 9 reactan t fc ^ a
0 n n s
0 0 03 -J
0 1

U t] ff ' ' N- (~\ Tt TT ' 1 Tj""" HN0 3 8.0 feAB 25 4.5 -5 * C)


.1 C -"- ^ "8 v.JH-ng * n H 20 10 2A = 1-4;
DO 00 -5
10 2B =2-100 HC10 4 3.4 25 7.2
HC10 4 0.01-0.8 fe= *o^x X
NaC10 4 0-0.8 > x=Cin_
LaC10 4 0-0.3 feQ 2. 12
rtr -5 CD
-5 at
Icio 4" 0.06-0.9. I 40 fc x 3.5 01
HN0 3 0.0&-51 fe = k +k^
NaN0 3 0-6 f X=NO ~40 ftb </. 1P
P AC -5
2N0 3" O.lJ 40 fcx 2.2 -5
0.2 40 -5
X
0.4 40 k x 1.5 -5
1.2 40 fe 1.0 -5
6.0 1.1
40 /I*X 2.5 -5
Cl" 40 -5
0.0 fcB
0.05 40 1.03 -5
0.2 40 2 -7
-5 * (8)
AC97* A= 1.0; B = 0.l NaC10 4 0 feAB 25 3.25
O.SO 25 3.40 -5
0.40 25 4.34 -5
0.60 25 5.35 -5

Research Council
December, 1955
National Bureau of Standards - National
Homogeneous Reaction Kinetics
312.422
0) k = A ~~
o 0
id tf c. 03
3 k x jQ n A x ion
E " E 3
3 0 Amount of Amount of d C
T C S 09 0)
No, React Ion Addend o o E
e reactan t addend c E t>
s 03 0. A 0
- O E k n n O
e ) O
t- _J
o

.8 CJL + Hg(OCOCH ) >C H HgOCOCH + CH.COOH M A = 0.93; &AB 50 7.5 -7 * (2)


O o 32 00 3 o
B - 0.095 70 5.72 -6
90 3.52 -5 22.2 7.6 8
A = 0.6-0.9; HC10 4 0.030 25 2.34 -5
B = 0. 1 0.046 25 3.50 -5
A = 0.2-0.6; 0.099 25 7.2 -5 (*)
B - 0.1 CO
A=2; B=0.3 0.29 25 1.00 -4 K
XJ
A = 0.07-0.4; 0,32 40 8.2 -4 ( 6)
B = 0.3
AC97* A= 1.0;B=0.1 0 25 4.2 -8 * (6) 3
Ofc
0.05 25 3.5 -6
0. 10 25 1.00 -5
0.20 25 2.66 -5
0.40 25 8.27 -5 CO
0.60 25 1.80 -4

Mono-alkyl substituted aromatic hydrocarbons

.5 CH 3 C 6H 5 + H 8( COCH 3) 2 * M A = 0.9; feAB 50 3.77 -6 * ( 2)


B = 0.09 70 2.47 -5
CH-C H^HgOCOCH, + CH.COOH
3 O 4 v v -4
90 1.27 SO. 3 2.1 8
A = 0.6-0.9; NaC10 4 0.09 25 1.28 -6
B = 0.09 0.13 25 1.73 -6
0.32 25 3.10 -6
HC10 4 0.030 25 1.58 -4
0.046 25 2.50 -4
A= 0.1-0.2; B == 0.1 0.098 25 5.59 -4 f 1)
0.4-1 0.09 0.09 25 5.2 -4
1.9 0.3 0.28 25 8.0 -4

National Bureau of Standards- National Research Council December, 1955


Homogeneous Reaction Kinetics
312.422
CO k - A =
CO 0> 0
CO t_
e "^ A* x lQn -M D
6 - -H fe x 10n -H
3 C Amount of Amount of C
Cti 4> d
TJ >
-o c
No. Reacti on Addend <o o OJ
g E
c 4)
0 reactan t addend CL
S CO . *-* X
V- O E fe 0
<r> a) H-
n n J
o

-6 / 2\
.4 M A = 0.9; feAB 50 1.16 *
GWs + Hg(OOOCHj
a A

O D 0
B = 0.09 70 7.9 -6
0-CH C H H00COOH + CH.COOH
364 3 3 90 4.14 -5 SO. 6 1.0 8

-7 ( ^\
M A = 0.9; feAB 50 4.96 *
.5 CH aC6H 5 + Hg(OCOCH 8) g * CO
B = 0.09 70 3.57 -6
m-CHJ:
364 3
H HgpCOCH,o + CHGCOOH -5
90 1.99 21.3 1.3 8

M A = 0.9; feAB 50 2.12 -6 *


( 2)
.6 CH 3 C6H 5 + Hg(OCOCH 3) 2 >
B = 0.09 70 1.32 -5
J
0C ITHgOCOCH-3 + CHCOOH
-CH 364
90 6.59 -5 19.9 6 7

h AB 50 3.25 -6 *
( 8)
.7 C 2H BC6H ft + Hg(OCOCH 3) 2 -> M A=0.6; B^O. 1
C 2H 5C6H 4HgOCOCH 3 + CHgCOOH

A=0.6j B~0.1 feAB 30 3.03 -6 *


f 8)
.8 (CHJ 0CHC H + Hg(OCOCH J 9 > M
3 * 0 O o *

o
(CHJ 0 CHCH HgOCOCH_9 + CH.COOH
3 , O

*AB 50 2.48 -6 *
( 8)
.9 (CHJ 0 CC H + Hg(OCOCH J _ ^ M A=0.6; B^O.l
336* 3 <6
(CHJ A CC H HgOCOGH. + CH COOH
3364 3

Di(tri) (tetra) (penta)-alkyl substituted aromatic hydrocarbons

feAB 50 1.26 -5 *
( 3)
.10 0-(CHJ 0C H A -- Hg(OCOCHJ ,, > M A=0.5; B^O.l
o 2 (J 4 o *
(CH 3) 2C 6H 3HgOCOCH g -*- CH g COOH

feAB 50 2.70 -5 *
( 8)
.11 -(CH 3) 2 C6H 4 + Hg(OCOCH 3) g > M A=0.5J B^O. 1

(CH 3) 2C6H gHgOCOCH 3 -f CH gCOOH

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
312.422

CO o fe = A =
to $ L. o
a 5 3 A x ion 05 u.
6 - -H fe x ion M
"*
\ ? O Amount of Amount of 3
d C -H
No. React 1 on '5 > Addend o c u
S o 40
tD O 0 E W
1 o reactant addend c o. E <D
2 CO E O H
>*-^ +- 0
fe A 0 .
<D 3 -o n n -1
O

.12 *~ (CH a) 2CAH * + Hg(OCOCH J _ > M A=0.5J B^O.l -6 ( 8)


O O O A
* AB 50 6.40 *
(CHJ 0C H HgOCOCH, 4- CH.COOH
*f o 3 3 8

.13 1>2,3-(CH 3) 3C6H 3 + Hg(OCOCH 3) 2 > M A=0.4; B^O.l feAB 50 -5 (')


5.33 * Co
(CH 8) 8caH^0ococH8 + cH3coor
(X)
.14 1,2,4-(CH 3) 3C 6H 3 4- Hg(OCOCH 3) 2 M A=0.4; B^O. 1 feAB 50 -5 ( 8)
3.93 *
(CHgJgCgHgHgOCOCHjj 4- CHgCOOH

.15 1, 3, 5- (CH ) C H 4- Hg(OCOCHj > M A=0.4J B~0.1 feAB 50 1.65 -4 * ( 8)


O if O O O

(CH g ) gC6H 2HgOCOCH 3 + CHgCOOH Oi


Oi

.16 l,2,3,4r(CH 3 ) 4C6H 2 4- Hg(OCOCH g) fl ^> M A=0.4; B^O.l feAB 50 1.00 -4 * ( 8)


(CH 3) 4C6HHgOCOCH 3 4- CHgCOOH

.17 1, 2, 3, &- (CH 3) 4C6H 2 4- Hg(OCOCH 3) 2 M A=0.4; B^O. 1 feAB 50 2.03 -4 * ( 3)


(CHjC
o 4 O
HHgOCOCH, 4- CH Q COOH
o o

.18 1, 2, 4, 5- (CH g) 4C6H 2 4- Hg(OCOCH8) 2 > M A=0.4J B^O.l feAB 50 2.36 -5 * ( 3)

(CHJ^C HHgOCOCH 0 4- CH^COOH


346 3 3

.19 (CH J _C H 4- Hg(OCOCH J 9 ~> M A=0.5; B~0.1 feAB 50 1.75 -4 * ( 8)


o 0 O <A &
(CH J .C.HgOCOCH. 4- CH COOH
350 3 3

National Bureau of Standards- National Research Council December, 1955


z.
o
is 2 8
ffi
0
O
e EC -5 K 0 w
l L- Oi
ac
K
"a MK + ^
oq OQ W
fO
+ -1- *
09a 0
1
8
o
1
O
co
1X 4 * on !
React
0
*
0) +
%
-1- ffi *++
u8 1
trj
8 8

R
"a
d Metrfal a:
o
3
O
I
tr
<
d
H (
droxy Med i um
0 2 P
ix
o CD o Mo
** O (Sol vent)
(ft
p.
0* 3>
*< II
koxy)
alsub
I
^ >M
5 !T
*<
CD
i "
II
w * T P*
^ 0
^ h* h- ^ " ^ 6 O
^ ^ O O CO GO Ol U
<w {
oojo^arooocD tutu (0 <r*
H 3>
CO 00 O> Ol OO g r*- n.
O5 ro c cyi CD O C 0
3 Q <r^ 3
<0 Q_
i ffi i p
To|
romatic-( be1nzene
f>3 a> I-* (-^ II
iU W ^3 tf^
11ia - o
-h
3*- Defined mass
^ ar
> > fe act? on 1 aw
rfa.^rfi.^^^J\D OflCdCdOajO On 0 0 0 0 Temp eratu r e
rorvDtorowrocn oooo?o
oi^wwrorocn t->H^^ro-<i j-j. O> -> C30 Ul
rKi^Hi-^ c> H1'
t_k t-jk. rfk, <3 O
i-j. 0 *0
B^H-^oio;^ !^o w pa <* -<i ** o
X
e "
i i i i i i i i i i i i i i i i i 3 3
B *3
C71
M- ^w ^
O O
w iw
III ^_^_~^ ^
<D 5 "
* * -H-
* Comments
"^a
^ -4 ^ O> Li terature
^01 *' *-^ '-^
Homogeneous Reaction Kinetics
313.422

CO k = A =
CO *
-M Of C0 k x io n m
3 /* x io n -M 3
Amount of Amount of *-
C
No. Reaction
* $
'9 * "0 C
0)
0)
Addend t> o S L.
re act ant addend o i
._ -H CL o
*~~~' >+- o 1
fe n /> o
C f n 3

.23 (C H ) Hg + HC10 > C H + C H HgCIO Et95* -3 ( 8)


* * 66 654 10 2A = 1.3-3J /I AB 43 7.23
10 2B = 1.6-2 47 1.14 -2
50 1.51 -2 21 1 12
Di 97.2* 50 3.91 -2
. CO
Di 96.8* 50 2.97 -2 24 4 14
DI 69.5* 10 2A = 1.6; 50 4.84 -3
-3
^
10 2B = 2.7 KC10 4 0.0125 50 7.71
0>
KC1 0.014 50 5.94 -3
0.028 50 7.49 -3 CO

Oi
CODED SOLVENTS
Ac97* Acetic acid 97% + H 20

DlOx* Dioxane
Di 97.2(96.8) (69.5)* Dioxane % indicated + H 20

Et95* C 2H 6OH 95^ + H 2

National Bureau of Standards- National Research Council December, 1955


Homogeneous Reaction Kinetics
312.422

COMMENTS

Reaction. (.1) Selected data. Units converted from origi total rate (.3) and ratio of products formed. For (.4) (.5)
nal minutes. First 10% reaction only. Second order rate values are twice the partial rate constants per hydrogen of
constants calculated from measured pseudo first order con authors and represent the actual rate of formation of ortho
stants by dividing by saturation concentration of benzene. and me ta compound. (.7) (.8) (.9) (.10) (.11) (.12) (.13) (.14)
Solution stirred vigorously and speed of stirring and volume (,15(.16) (.17) (.18) (.19) Rate law followed from 30-70%
CO
of C oH O did not effect measured rate. Correction made for reaction. Units converted from original minutes. All rate
slight extraction of L from H 20 layer. Rate apparently de constants corrected for small parallel reaction with solvent.
pendent upon total perchlorate ion andnotupon Ionic strength See 312.421. (.20) Units converted from original min CO

or perchloric acid. Similar behavior with sulfuric acid. utes. Snail amount of urea added to remove oxides of nitrogen.
Slight negative salt effect on catalytic constants of nitrates. (.21) Pseudo first order rate constants as B in large ex
Second order rate constants in presence of (C ftH
254
) NNO 3 , cess. Tltrlmetric method for L and spectrophotometrie for
markedly low, may be due to complexing of C 6 H 6 with positive A give consistent results. Dllatometric methodof ( 4) gives
ion, (C aH ) 4N"*\ (.2) Second order rate law up to 80% appreciably higher values. (.22) Pseudo first order
reaction observed by (*) Indicates polymercuration unimpor rate constant followed up to 85% reaction and second alkyl-
tant. Units converted from original minutes. (.3) Only mercury bond resistant to cleavage up to 20 half lives for
early stages of reaction followed to avoid polymercuration. first bond. In presence of HG10 4 oxidatlve side reaction
Rate represents parallel mercuration at all available posi occurs with solvent after about 40% reaction which increases
tions. For reactivity at each position see (.4) (.5) (.6). acidity and metallic mercury separates. Dllatometric method
Reaction followed by tltrimetrie method for B and by infra of ( 4) gives appreciably higher values than titrlmetrlc
red spectra analysis. Units converted from original minutes. method for L or spectropho tome trie for A,
(.4) (.5) (.6) Units converted from original minutes. Rate
constants calculated for these three parallel reactions from

National Bureau of Standards - National Research Council December, 1955


Homogeneous Reaction Kinetics
312.422

CO

LITERATURE
CO

(*) H. C. Brown, C. W. McGary, ACS 1955, 77, 2300. ( 2) H. C. Brown, C. W. McGary, ACS 1955, 77, 2306. ( 3) H. C.
Brown, C.W. McGary, ACS 1955, 77, 2310. ( 4) A.H. Corwln, M. A. Naylor, ACS 1947, 69, 1004. ( 5) F. Kauftnan,
A.H. Corwln, ACS 1955, 77, 6280, (6) R.M. Schraram, W. Klapproth, F.H. Westhelmer, JPG 1951, 55, 843. (7) S. Wln-
steln, T. G. Traylor, ACS 1955, 77, 3747. (8) F.H. Westhelraer, E. Segel, R. Schramm, ACS 1947, 69, 773.

National Bureau of Standards- National Research Council December, 1955


Homogeaaous Raac tiona EXCHANGE Liquid phase

312.45! Nitration of Aliphatic Compounds Amounts are in M/I.

k =

Amount of Amount of Defined mass


No. Reacti on
react ant addend action law

CO
a
.1 CC1 A= 0.05-0. 4; B= 0.09-0. 4 0.004-0.2 dL/dt=feAB/(0.02 -H X*) 30 6.4 -5 21.5

C6H llN 2' C6H llN 2' HN0 3


dM/dt=fe AB/ (0.02 + X*) 30 7.1 -5 21.5
(L) (M) (N)

CO
01
05
COMMENTS

Authors suggest mechanism for reaction involving free radicals but not a chain reaction. The constant 0.02 in the
CH'.
^, and N0 2 for reaction with CflH
rate law is a measure or the competition between solvent, CCl, 11' The reaction with CC1
leading to formation of C -H Cl and oxidation of solvent with formation of CC1 3NO phosgene. [ceH uCl 2,5,
32

LITERATURE
J. C. D. Brand, ACS 1955, 77, 2703.

National Bureau of Standards - National Research Counci I December, 19 56


Homogeneous Reactions EXCHANGE Liquid phase
312.452 Nitration of aromatic compounds Amoun ts are in M/ I ,
Rate constants are in
M/I and sec.

Coded solvents and coded addends are at the end of the table.

k =
Supp
i
t
1ng
emen
Tempe
aturer k * & .4 >< ion 1
Comments Liatureter
1951
No. Amount of Amount of Def i ned mass
No. React ion Sot vent Addend
re act an t addend act i on 1 aw
n n

.16 . 1 C_H + HNO M + H-SO. 68.0 % A B = 0.61 2.6 -2 *


(9)
DO O
kA 25
66.9 25 1.3 -2
C H N0 0 + H 00
852 2 -3
64.2 25 1.5
61.6 25 1.4 -4
59.5 25 4.2 -5
57.3 25 1.4 -5
-6 CD
54.0 25 1.9 Ol
51. 1 25 4 -7
-4 * ( 14>
CH COOH 99.8 % A=0.35;B= 12,4 HN0 2 0.5 feo =dL/dt 11 9.7
3
0.10 8.0 0.001-0.004 kA 20 1. 19 -3
0.10 9.7 0.46 20 1.67 -3
0.17 9.7 0.46 SO 1.35 -3
0.21 9.7 0.46 20 1.24 -3
0.34 9.7 0.46 20 7.5 -4
*
( 14)
CHgNOg A=0.1;B=3.0 HN0 2 + 0.0034 1 -dA/dt = fe + *' H 2S0 4]
H 2 S4 0-0.045J -10 k = 1.04 -6
-10 V = 1. 45 -3

cci 4 A^ 2.36;B'X'0.03 * C 11)


.17 C6 6 2 5
BzOH = C nftH oKGOOH; Bz fiO = (C 6H 5CO) 2
BzOH = 0.063 Bz 20 0.035 bB 20 2. 11 -3
C K^0 2 + HNO g
H 0.075 20 1.23 -3
ft 0. 144 20 9.35 -4

National Bureau of Standards - National Research Council December, 1956


Homogeneous Reaction Kinetics
312.452
O)
c h = A
Teremperatu A x
k x i Comments L
i
terature
9 Z Amount of Amount of Defined mass
No. React i on Solvent Addend i
reactant addend acti on 1 aw A
Q. n n
3
CO

.17 C^ + N a0 0 -^ cci 4 BzOH = 0. 127 BZ 20 0.035 feB 20 1.07 -3 *


()
0. 127 0.102 20 7.74 -4
C continued)

.18 .2 C6H 5CH 3 + HN3~> CHgCOOH 99.8 % A=0.33;B= 12.4 HN0 2 0.50 -dA/dt=*o 11 1.03 -3 *
( 14)
0.05-0.2 7.0 0.00 2-. 006 20 6.3 -5
CH 3 C6H 4N2 + H 3 (")
CHgCOOH 90 % A B 45 (only re lativ B rate) CO
56.5 % (2); 3.5 % (3) HN0 2 + 0.079 K
40.0 % (4) X
-10 -7 ( 14) 'O
GH gN0 2 A=0.155 B=3.0 H 2 S4 0 5.3 *
r*-j
k0
0.014 -ID 1.28 -6 0>
0.042 -10 7.12 -6 3
0)
0.063 -10 1.41 -5 3
-5 r+
0.084 -10 1.86
A=0.09; B=7.0 HN0 2 0-0.08 kQ = (a + b [HNOJ*)- 1
a -6 8.2 +3 <D
C7!
b -6 7.6 +4 Cfc
0.0038 h0 -6 7.78 -5
0.076 -6 3.45 -5
0.170 -6 1.84 -5
0.420 -6 7.0 -6
A~0.1; B=7.0 HN0 2 + 0.001-.002 k = 0(1 + >[H OO r1
HO 0-1.6 a -10 8.8 -5
2
b -10 1.3 0
HN0 2 + 0.0046
A=0.1; B=7.0 KC10 4 0 k0 -10 9.78 -5
0.011 -10 1.03 -4
KN0 3 0.0065 -10 6.58 -5
0.0123 -10 4.30 -5
HN0 2 + 0.001-.002
KN0 3 0 -30 8.89 -5

National Bureau of Standards - National Research Council December, 1956


Homogeneous Reaction Kinetics
312.452
en
c o fe = A =
i. o
OJ u
c 3 fe x ion 4 x ion +J 3
-H +J
Amount of Amount of Defined mass ctt c
No. o J
React i on Solvent Addend L. i i_
0 E
react ant E fi
ii GKa addend act! on 1 aw Q. k A
iH n n cS
3 i
t -J
CO

HN0 2+ 0.001-.002
.18 .2 uwn ^ -10 -5 ( 14)
G6H
r1 P 5CH
PU 3 +
-4- HN8 CH 3N0 2 A=0. 1;B= 7.0 KNO 0.0035 4.78 *
3 k0
0.023 -10 2.18 -5
(continued^
0.043 -10 1.87 -5
0.28 -10 1.30 -5
0.63 -10 9.4 -6
CO
-5
K
.19 .3 C 6H 6 C 2H 5 +HN 3 * CH^COOH 99.8 % A=0.04;B=7.0 HN0 2 0.0027 -dA/dt = k o 3D 6.00 * (^ T3
o T3
0.10 0.0046 3D 6.20 -5 t**j
CHCHNO +HO
25643 2 -5 CO
0.10 0.0143 20 5.65
3
CO
5J
6.4 ))( 8 )
.20 W< CH 3> 3 + HN3-^ CHgCOOH 90 % 45 -1 ( rate i-elatJLve tc ) (.Ifi cs.

K*.
<0
>11.7 % (2); 8.5 % ($ ; 79.8 % (4) Oi
Oi
(7)
.21 C.H.OCH, CH 3 COOH A=0,026; B = 4.93 HN0 2 0.691 feA 21 4. 14 -3 *
t> O O
+ HNO,O >
CH gOC eH 4NO a + H gO
M--H 2S0 4 62.8 % A B = 0.61 (NH 2) fO 0.07 teA 25 3.0 -2 < )

59.6 25 4.0 -3
57.3 25 9.8 -4
53.5 25 1.1 -4
49.5 25 1.5 -5
45.2 25 2 -6
41.3 25 4 -7

( 12)
cci 4 A= 1. 50; B= 0.043 feAB 15 1.34 -3 *
.22 C OH O COOCH,u + N 90 OR >
1. 21 15 1.42 -3
CH OOCC H N0 0 + HNO_
3 6 4 * o 15 1.53 -3
0.83
0.64 15 1.63 -3
-0 15 1.82 -3

National Bureau of Standards - National Research Council December, 1956


Homogeneous Reaction Kinetics
312.458
O>
C k = A
Temperature smmon
Cot tereratu
Li
Amount of Amount of Defined mass k x 1C A >< 10
No. React I on Sol vent Addend i
r e act an t addend action 1 aw
Q. ** A
n n

.23 WOOCA + HN0 3 - CH COOH 99.8 % A=0.1D;B= 10.5 HN0 2 0.0029 feA ao 1.55 -4 ( t4)
3
C H OOCC H NO + H 0
25 642 2

.24 C H COOCgH + NgO ^ cci 4 A= 1.35; feAB 15 1.44 -3 * ( ia)


1.08 o 15 1.53 -3
C 2H 5OOCC6H 4N0 2 + HN0 3 CO
0.80 cb 15 1.70 -3
o -3
0.55 o 15 1.87
-*o n 15 2.17 -3
0.5 m 20 4.41 -3
3 i
C55
CO ( 12) a
.25 C 6H 5COOC(CH 3) g + N g0 5> cci 4 A = 1. 07; S kAB 15 2.07 -3 *
0.73 15 2.38 -3
(GHJ.OOOCC H N0 0 + E
33 642 15 2.54 -3
0.57 o
-0 H 15 3.02 -3
PQ Q)
( 13)
.26 kA 40 3.33 -4
C H_OH_9L)_Na ~> HNO _ '^ M + H 2S0 4 18.7 mol % A=0. 164; B= 7.0 mol %
Na80 3CH 2C 6H 4N0 2 + H 20

> 14 % (3)
___ Mol %
-3 * ( 13)
.27 H CH QCH 0SO Na + HN0 30> M + 17.2 m'ol #B
C 65223 A = 0.169 NaC104 0.00 kA 30 2.48
0.32 30 2.80 -3
9 2 264 2 2 0.57 30 3.15 -3
1.06 30 3.93 -3
NaN0 3 0.63 30 2.22 -3
1.09 30 2. 13 -3
2.12 30 1.87 -3

National Bureau of Standards- National Research Council December, 1956


Homogeneous Reaction Kinetics
312.452

Supp
i
tementng k = K
1
Temperature I
Comments
1951
No. k x 10 ion
Amount of Amount of Defined mass L
i
tereratu
No. React i on Sol vent Addend S
r e ac t an t addend action law
k n A n

.27 'A^CWa+HNO^
(continued) Mol % M Mol$HC10 4 Mol % B; A = 0.169 mol ratio kA * ( 13}
75.5 7.8 16.7 M/B = 82/18 30 1.16 -4
75.1 8.3 16.6 n 30 2.68 -4
74.0 9.6 16.4 n 30 7.48 -4 CO
73.4 10.3 16.3 n 30 1.45 -3 K
T3
"X3
73.0 10.9 16.1 n 30 3.00 -3
r-J
76.6 7.7 15.7 M/HC10 4 90.8/9.2 30 9.9 -5 CO
74. 1 7.5 18.4 n 30 2.33 -4 3
CO
72.7 7.4 19.9 n 30 4.30 -4
71.3 7.2 21.5 n 30 7.18 -4
69.7 7.1 23.2 30 1.87 -3
67.8 25.4 n 30 4.80 -3
6.8
76.5 11.3 12.2 87.2/12.8 30 4.32 -4
11.0 14.1 n 30 9.33 -4
74.9
15.7 n 30 1.97 -3
73.5 10.8
16.9 n 30 3.30 -3
72.5 10.6
17.2 SO 8.15 -4
72.6 10.2
n n n 30 2.48 -3
it n 40 6.22 -4 17.4 8 9
-4 ( 6)
73.8 9.8 16.4; A= 0.08 25 4.53
25 2.30 -4
73.8 9.8 16.4 0.84
-dA/dt=feo 0 1.07 -4
60.0 0 40.0 0.53

-3 * ( 9)
M + H 2 S0 4 85.0 % A B = 0.61 feA 25 9.0
.28 C 6H 6C|N + HN0 3 >
25 3.5 -3
84.0
NCC 6H4N0 2 + H 20 1.5 -3
83.0 25
25 5.1 -4
82.0
25 1.9 -4
81.0
25 1.0 -4
80.0

National Bureau of Standards- National Research Council December, 1956


Homogeneous Reaction Kinetics
312.452
en
c <D h = A
l_
-H ^ 3 A x 1
Comments 1
Li
terature
H k x ion
0 Z Amount of Amount of Defined mass ftf
No. React ion Sol vent Addend l_
0
re act an t addend action law a.
i
K-
n n

.29 w^.*;-;-7B M + H 280 4 100 % A=0.05;B = 0.03 feAB 25 8.1 -3 ~ *(' \ / 10\
0.30 0.03 25 1.2 -2
3 642 -2
L 100 0.50 0.03 25 1.4
100 2.5 0.03 25 1.19 -2
100 A = B =0.025 25 8.5 -3 CO

99.5 25 9.3 -3 ~15 1 9


98.3 n 25 1. IS -2
96.6 n 25 1.57 -2
96.6 A = 0.025; B = 0 .05-0.07 25 1.64 -2 00
96.6 0.10 25 1.59 -2 r*
94.7 A = B = 0.025 25 2.16 -2
91.0 n 25 3.48 -2
w -2 to
88.4 25 2.66
87.5 n 25 1.65 -2 13.4 1.0 8
86.5 n 25 7.43 -3
85.9 n 25 4.78 -3
84.7 n 25 1.76 -3
82.0 " 25 1.71 -4
-3 ( 10 )
H 90 + SO 2.8 % 25 9.5
5.5 25 1.13 -2
7.5 25 1.33 -2
10.3 25 1.53 -2

.30 .8 W>. - "NO, - B A= o.ao HN0 2 0.001-0.2 fcA; k = (a + b[ HNOjV 1 * ,,


a -is 1.7 +2
b -13 2.5 +2
B + M 3 % A=0.21;M= 1.65 HN0 2 0.1-0.26 feA; fe= (a + t>[HNoJ 3/2)-l
a -13 3.0 +2
b -13 2.5 +4

National Bureau of Standards - National Research Council December, 1956


Homogeneous Reaction Kinetics
512.452
CO k =
c A =
A x 10n 09

L.
k x 10 4- 3
12 Amount of Amount of Def i ned mass C +J
No. React! on Sol vent 0) 40
i "-1 Addend i E i.
react ant addend act! on 1 aw E
13 . , Q .Q
fr-*
X n n c3
3 1
CO

feA; k = (a + b[i NOJ 8/ 2)" i


.30 .8 C 6H 6N2 * HN3 > B + M 5 % A-0.3DJM- 2.93 HN0 8 0.001-0.3 a -13 5.0 +2 * ( )

(continued) b -13 4.0 +4


B + M A=0.07-0.l4M=0 HN0 2 0.040 fcA -13 4.68 -3
0.40 n -13 3.54 -3
0.89 n -13 2.76 -3
CO
2.10 H -13 1.57 -3
3.19 n -13 7.7 -4
0.02 2.5 HN0 2+ 0.02
KN0 3 0.0 -13 6.00 -3
0.11 -13 5.32 -3
0.21 -13 4.11 -3
0.32 -13 2.96 -3
M + H 2S0 4 97,4 % A=0.0&-0. 1; B=C .03 hAB 25 1.58 -2 (*) ( 5)

86.7 25 2.23 -2 Oi

( 4)
.31 C 6 D 6N2 + HN3 * M + H 2 S0 4 97.4 % A= 0.05-0.1; B=C .03
C feAB 25 1.97 -2 *
86.7 25 2.14 -2
C6D4 (N0 2) 2 H- DOH

-2 (g)
.32 .4 C H F + HNO > M + H 2 S0 4 70.0 % A B = 0.61 feA 25 1.3 ^
Do 3
68.4 25 7.0 -3
FC H N0 0 + H 0
642 2 -3
68.0 25 4.0
66.4 25 9.9 -4
64.4 25 2.0 -4
62.8 25 5.3 -5
59.6 25 8 -6
54.0 25 4 -7
-4 ( 14)
CHCOOH 99.8 % A=0.1-0.2JB = 8.0 HN0 2 0.004 *A 20 2.6 *
3
9.0 0.004 ao 1.1 -3

National Bureau of Standards - National Research Counci I December, 1956


Homogeneous Reaction Kinetics
312.452
OJ
c fe = A_ 0
A x ion m u
fe x 1C n -H 3
I* Amount of Amount of Defined mass H
g (fl
No. 1 * React i on Solvent Addend i 1_
* m 4>
reactant addend acti on 1 aw . fe A O -+-"
s n n o
3 i- -J
W

,33 .5 CHC1+HNO - W + H 2S0 4 72.0 % A B = 0.61 feA 25 4.7 -2 * ( 9)


70.0 25 7.7 -3
C1C H N0 0 + H 00
642 2 68.4 25 3.0 -3
68.0 25 1.7 -3
64.4 25 8.4 -5
62.8 25 2.7 -5
59.6 25 2.5 -6
CO
57.0 25 7 -7
CHCOOH 99.8 % feA 30 5.2 -4 (")
A=0.10;B = 9.0 HN0 2 0.0043 *
3
0.05 10.0 0.0022 30 3.65 -3
0.10 10.0 0.0022 30 3.25 -3
0.23 10.0 0.0022 20 2.94 -3
0.30 10.0 0.0022 30 2.81 -3
0.10 10.0 0. 101 30 1.19 -3
0.10 10.0 0.135 30 6.14 -4
-4 Oi
0.10 10.0 0.160 30 4.18 Ob
0.10 10.0 0.203 20 1.50 -4
0.10 10.0 0-0.08 feA; fe = (a + fcfrINOJV 1
a 30 2.40 +2
6 30 1.47 +3

.34 .6 feA 25 4.5 -2 * C)


C Do
H Br + HNO oa > M + H 2 90 4 72.0 % A B = 0.61
25 7.3 -3
70.0
BrC 6H4N0 2 + H aO -3
68.4 25 2,7
25 1.60 -3
68.0
25 7.2 -5
64.4
25 2.3 -5
62.8
25 3 -6
59.6
25 7 -7
57.0
-4 ( 14)
GH 3COOH 99.8 % A-0. 10;B = 9.0 HN0 2 0.0043 feA 20 4.5 *
0.0043 30 3.9 -4
0.30* 9.0

National Bureau of Standards - National