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Monograph 34_-__________-______----___,__--_.____ 2. 75
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
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
in
Homogeneous Reaction Kinetics
SUBJECT INDEX
Table
3oo EXCHANGE-SUBSTITUTION , mie of Tabl \
(number of pages) number
IV
Homogeneous Reaction Kinetics
V
Homogeneous Reaction Kinetics
SUBJECT INDEX
VI
Homogeneous Reaction Kinetics
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
VII
Homogeneous Reaction Kinetics
<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
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.
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
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
COMMENTS (continued}
CO
(Si
Oi
Oi
LITERATURE
C 1) j. D. Brandner, H. G. Urey, J. C.P. 1945 13, 351.
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
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.
ctf ctf
k x iOn 10n
Amount of E
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
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
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.
No. Reaction
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
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
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
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.
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.
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
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.
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.
A =
A x 10
Amount of
No. Reaction Addend
reactant
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
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
L. __-
LITERATURE
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
.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
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
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-
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
]
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
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
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
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.
.12 d-C 8H BCH(CH 3 )CH 8CH 8CH 3 + DgS0 4 A A sat. with B " FE 60 1.0 -5 *
( 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)
= 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
-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
-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
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
.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
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 *
Na+ -1 (18)
10 2A=1.3; 10 DB=3.1 =B feAB 20 2.07 *
.70 CHCl g + OD~ D20
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
-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
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
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.
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.
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 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)
.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)
*
-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
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
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
.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
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
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
72.7 25 5.6 -7
76.4 25 1.48 -6
Anthracene
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.
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
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.
.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
.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
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.
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
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
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
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
(') 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
.17 -ClC H COOH + H O 18 D133* not stated HC1 0.064 feAfe4] 80 1.1 -4 * ()
64 2
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
.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
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.
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.
^-
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 "
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.
k = A =
A x I
Amount of
No. Reaction So I vent -o c
Asf
a, o
reactant
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.
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
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
.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
.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
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
reactant addend 0
n A n
I
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
-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
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
.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
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
-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
-7 ( 36,
.53 c;yclo-c 15H 29 l + i*"" C 2H ROH fe AB 25 (9.9) 20. 1 6 8 *
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
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
.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
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)
( 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
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
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
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
.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
.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
.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 }
.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
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
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
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
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.
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.
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
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
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.
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.
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
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
.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
* 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
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
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.
aj n^B JO} j -|
I S} U9UJUJOQ *
C
O5 O ^ f
C\2 C\2 ^
N 9 8 2 f
- *
se c ^ <** to to
1 III
CM
x Jg - ^ co co
^05 o
0 ^*
^ i>
*"
^ >
...n^.d-.i
a p| a 8
o (0
0) f
sa % 5
j*
5
JSt
-l- E 3 S S
ec "H
-C
o
<B
c
0
E
"- '
*H
0
"H
0
]!>
v
+
^1
^
0 O
CL C HN *H *H -^w >-^ vH
M- 0 O
0 Of
Q "* o> CD -** cq <D CD
P. P.
H H a;
O o -o emical emical
o S S g
LU c sQ> s 3CO S
-s
" 1
CD o 5
^
&
J 00 H O
- t S O TO 0 0 .
CO 1 00 TH O o
pueppy Q. o.
o ~
+ -o 4-
o
,.
~JI
UD LO TO TO ^ U? CD 9
PQ" VT ^ TH g ^ W a? - to to
as -H1 ***
CD t
11 " e e >> " " ^ ^
O
II ^PQ
W'*
O
f-t
O
f_
r-l -<!pQ-<tJPQ
ce* w
| |
CO
Q.
CD
P. Pi
PQ _. PQ
P.
PQ +
* tXt '
Pi
C P. -1- 1-
PQ
O P. PQ
P^ PQ O CO CO
-H P. PQ K o
g g
Pi ^-. CO CO
g"
O PQ
0) pq P< pq + + co
OJ PQ PS
f t A,f
or
+ + S 3
5- f f F t
t f 1 1 t s~
0)
p. CO
PQ Vf-
' W r W + H- o
acj CQ Pt
PQ PQ
-f +
O
co
g CO
o
CO
. c> "^co CO n
g g g 0N S 5 g
r-4
H ^ W tO
o O ^H "H . CO to
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
( 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
.7. 1 C1CH + Br >C1 C- + HBr (From .7 and phot ochemlcal reaction) k AB 147- 182 9.3 2.3 9
3 3
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$. It is possible that another
-dB/dt = competing reaction for (CH ) 3 O such as (CH 3) O >
1 +
COMMENTS (continued)
CH 3 + CHCH-'CH
J
should have been included in the reaction finned. (.5)
Only initial rate, extrapolated to zero
mechanism. Inhibition by oxygen demonstrated. (.3.2) time. Inhibition by oxygen shown and inhibition by M demon
Variation in ratio of fc/^ by 30$ 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.
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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
> 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
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.
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
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
-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
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
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
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
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
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
Oi
CODED SOLVENTS
Ac97* Acetic acid 97% + H 20
DlOx* Dioxane
Di 97.2(96.8) (69.5)* Dioxane % indicated + H 20
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
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.
k =
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
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.
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
.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
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
.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
> 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
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
.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
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
-4 * (U)
.35 .7 C.HI + HNO, > CH COOH 99.8 % A=0 1-0 2IB = 8 0 HN0 2 0.004 kA 20 2.8
60 3 O
9.C 0.0043 20 1.37 -3
IC.H NO + H 0
O * * *
-5 * f 1 *)
.36 MCH 3) 2 C6H 4 + HN0 3 --- CHgCOOH 99.8 % A=0.01; B=7.0 HNO 2 0.0046 dL/dt= feQ 3) 6. 17
0.07 7.0 0.0192 20 5.70 -5
, . -f H 0
32632 2 0.0096 20 4.33 -6
0.06 5.0
-3 ( 18 )
.37 -CH 364
C H COOCH o + NO * cci 4 A= 1. 1; B=0.03 ftAB 15 1.58 *
* O
0.9 0.06 15 1.81 -3
CH C H (COOCH )NO + HNO. -3
363 32 3 0.6 0.03 15 1.86
- 0 15 2.18 -3
K*
* ,12% CO
feAB 20 2.9 -3 * Oi
.38 o-(C H OOC) C H + N 0 > CH 3GN A= 1.1; B=0.05
-3 Oi
0.8 0.05 20 3.07
(C^OOC) 2C6H 3N0 2 + HNO,
CHgN0 2 + CC1 4
33 2.70 -3
vol. ratio =9: 1 0.8 0.05
20 2.27 -3
7:3 0.8 0.05
20 2.02 -3
5:5 0.8 0.05
20 1.40 -3
1:9 0.59 0.06
20 1.43 -3
0.74 0.05
20 1.39 -3
0.90 0.05
20 1.31 -3
1.20 0.05
l8) f 90 )
feAB 25 1.08 -1 13.7 2 8 *r
.39 ^ovwioy.+ + .-> M + HLSO, 81.7 % A = B = 0.1
2 4 -4 17.6 8 9
L_ ^R n 25 4.07
3-N0 2-4-CH 3C6H3N(CH s) 3+ + H 20
0 * = fa =
u 9
^ x ion M U
3 fc x ion -M
Amount of Amount of Defined mass 4- 3
10 C M
No. Reacti on Sol vent Addend U S e 5
> U
reaotant addend action 1 aw g O
fe 4 V
1 n n a
h- -J
.41 -N0 0C H OH + HN0 0 > CH 8COOH 30 2A= 2.5JB=2.70 HNO a 0.55 21 3.1 -3 *
o 4 3 .A^O; C)
(continued) 1.38 0.38 21 3.6 -3
B = 1.4-5.8 0.1-1.8 fc = a-6[HNOj
a 21 4.2 -3
b 21 4.5 -4
10 2A=2.5;B= 10 HNO a 0.1 21 1.20 -2 CO
V
0.5-1.0 21 5.0 -3
.42 ^"CIC^H^OCH^ + HNO A > CHgCOOH A=0.08;B=4.44 N 24 0.0375 fcA 2.61 -3 * (>
048 9
N 24 0.01-0. 03 1 *- fo BoJ()^2 + fcjt/ [NO"])
2 e 3 3 2 -2
(CH 8) 4NN0 3 0.007-0.08 f k2 35 1.3
0.01-0.02 J kf 35 2.5 -4
1D 8A=3-8;B=4. 14 HN0 2 0-0.34 25 5.2 -3 * (7)
1D 2A=6;B- 4. 2 HNO a + 0.04-0.08 Or
LINO o 0 35 1.59 -2 Oi
0.040 35 1.33 -2
0.081 35 1.03 -2
0.16 35 1.24 -2
0.24 35 1.45 -2
0,38 35 1.77 -2
10 2 A=6;B=4. 1 HNO g + 0.1-0.16
KN0 3 0 35 1.40 -2
0.055 35 1.27 -2
0.076 35 1.22 -2
0. 114 35 1.12 -2
0.152 35 1,09 -2
0.228 35 1.18 -2
.42 ^-CICLH.OCH-
6 4 o
+ HNO 3 > CH 30COOH 10 2A=6;B=4. 1 HN0 2 + fcAtHNOj *
(7)
1.31 _o
(continued} H 20 0 35
0.11 35 1.21 -2
0.22 35 1.11 -2
0.44 35 1.01 -2
0.89 35 0.93 -2
1.11 -35 0.94 -2 CO
10 2A=5;B=5.94 HN0 2 0-0.14 k^ + feA[HNOj
k 25 1.8 -4 (see comments)
h 25 5.8 -2
10 2A=2JB=9.05 HN0 2 3.5 x ID"" 4 dL/dt = feQ -15 9. 1 -6
7.5 x ID" 4 -15 9.6 -6
0 -11 2.2 -5
0 -5 3.6 -5
2. 5 x lf 4 -5 2.4 -5 co
5.5 x 10" 4 -5 2.0 -5
9.5 x ID" 4 6 1.7 -6
o k = j| =
L. 0
^ x ion CO L.
+*a
k x J0n M 3
C 4-
Amount of Amount of Defined mass OS
No. k. o
Reaction Sol vent Addend J E L.
9 1 0
react ant addend action 1 aw 0. E -H
i fe n A n 3
- _J
.45 /i ^ -5 (")
r pi ^*-"
* n vm _ 4.
u -WU uvrrv _
~ rLNU ^^ B A = 0. 15 HN0 2 0.03 .A 20 1.37
642 3
M^H 2S0 4 97.4 95 A=0.05JB=0.03 *AB 25 1.74 -3 * (*) ( 5)
) -H H 20
H (NO 22
C1C 63
95.6 0.02 0.02 25 3.52 -3 n'
92.0 0.02 0.02 25 5.48 -3
90.0 0.01 0.01 25 6.85 -3
CO
86.7 0.05 0.03 25 2.37 -3 ( 4) ( 8 )
-4 ( 10 )
H S0 4 + SO 0.0 % A = B = 0.025 25 9.6 *
2.80 25 4.9 -4
5.38 25 3.4 -4
-4 CO
10.93 25 1.90
14.6 25 1.26 -4
19.7 25 6.7 -5
-4 ( 12)
.47 0-C1 2C6H4 + N 80 B > Cd A= 1.4258=0.043 feAB 15 7.71 *
1.11 0.043 15 8.03 -4
2C6 8 + 3 0.88 0.043 15 8.19 -4
0.61 0.043 15 8.25 -4
-0 0.043 15 8.5 -4
.48 _ SY\
n Ux
r\ TJ
\^ 11
A. TTVJA
' rUNU
^
CH.COOH 99.8 % A=0.10;B= 10.5 HNO g 0.0029 A 20 4.98 -4 (")
3
^ O^O O **O
V
k = A =
l_ c
3 fc x I0n AQ x ion to 1_
-H -H 3
Amount of Amount of Defined mass cd C M
No. Reaction So 1 vent Addend i_ i O (0
<D E k.
re act ant addend action 1 aw Q- 6 O
fe A H
t
n n 3
_/
.50 ^" G1 2CaH 4 + HNa * CITCOOH 99.8 % A=0. 10; 8= 10.5 HN0 2 0.0029 fcA 20 2.00 -4 * (">
3
12.0 0.0030 10 6.76 -4
Cl C H JJO + H 0
2 6 31 2 2 -3
12.0 0.0030 20 1.65
12.2 0.0034 20 2.23 -3
CH 3N2 A=0. 1-0.38=8.5 HN0 2 0.0018 *A 20 6.49 -3
0.048 20 2.55 -3 CO
0.083 20 1.87 -3
0.106 20 1.00 -3
0. 174 gO 4.5 -4 CD
0-0.08 * = (a + 6[HNOJ^ r1
a 20 -Hi
4,0
b 20 1.6 +3
A= 0.1; 8= 8. 5; HN0 2 + 0.008
M = 0.3 KN0 3 0 fcA 20 6.49 -3 CD
Cn
0.010 20 3.48 -3 Oi
0.025 20 1.93 -3
0.061 20 1.11 -3
0.081 20 9.7 -4
o
h = A =
i_
A x ion v> v_
3 fe x ion H 3
H 4-
Amount of Amount of Defined mass C
OS 0 <d
No. React! on So 1 vent Addend U S E L.
0 E C
re act ant addend act i on 1 aw D. 0 M
6 k n A n 0
o _J
h-
C -4 * ( 12)
.52 -ClC6H 4Br + N 20 6 > cci 4 A=0. 5- 1.2;B=0.0 4 kAB 15 5.5
CLpBrC H N0 2 + HNO g
-4 * ( **h
.53 cci 4 A=0.4-0.7;B=O.C 4 kAB 15 5.7
"??-.
National Bureau of Standards - National Research Council December, 1956
Homogeneous Reaction Kinetics
312 452 16
O)
C 0 k = 4 =
L. 09
3 fe x ion 4 x ion -H
C ' 3
Amount of Amount of Def i ned mast C -H
(0 O
No. E H Reaction Sol vent Addend L.
0)
S E 2
- ^ r e ac t an t addend action law O. E
O H
^ iH >o X O
O. i
h-
n n _J
CO
.54 1,3,MCH 3 ) C H +HNO q * CH COOH 99.8% A = 0.05-0.1; HN0 2 0.004 dL/dt = k 20 5.62 -5 (")
3 o o o B^ o
B = 7.0 0.007 20 5.48 -5
(CH ) C H NO -H H 01
A=0.07;B=5.0 0.014 SO 4.17 -6
CO
2 1__
.55 3,MCHJ,C H,CH,80 fe/ 0 4.60 -3 * ( fl)
o o o o
~+HNO,o M + B Mol %= 39. 8 A= 0.11
dL/dt = * 0 1.81 -4
S0 3"CH 2-(CH J) 8C6H aNO a + H aO *'* '^ CO
0 1.47 -4 3
(X)
17.6 0.07 HC10 4 6.6 Mol* fe iA 25 5.9 -4
17.6 0.19
12 Q -4
0. O
11.7 90 9.0 -5
16.6 90 8.2 -5
0.026 feA 50 7 -7 * t 20 )
.57 2, 4r (NO ) C H OH + HNO g ~-> M + B 50 % A = 0.0012 HN0 2 CD
(*)
" w" I
A= 0.001 HN0 2 0.027 feA 50 2.3 -5 * CO
,58 2,6-(N0 2) 2C6H 3OH + HN0 3 --* M + B 50 %
-5 Oi
60 0.0065 50 1.7 Oi
(N 2' a e 2 2 0.029 50 5.7 -5
0.108 50 1.8 -4
-3 *
(">
,59 1-N0 2C6H 3:(CO) 2:C6H4 + HN 3 ^ B A = 0.24 HN0 2 0.0055 feA 30 2.48
n 0.0085 20 2.53 -3
H 2so 4 = 0.044;
n 0.0090 20 3.09 -3
0.101
n 0.0065 20 4.19 -3
0. 176
n 0.0070 20 5.03 -3
0.234
-4 * / 14\
.60 CH 0CX)OH 99.8 % A=0.10;B= 12.2 HN0 2 0.0034 20 1.80
l,a4-Cl 3C6H 3 + HN0 3 3
0.0018 33 5.44 -4
A=0.10;B=8.5
-4 / 12\
k AB 15 6.82 *
.61 CT/NM 9* A=0.55;B= 0.049
<e O
1,2,4-Cl 0 C 0 H w + NO
15 6. 19 -4
0.70
r*i r* H NO 4* HNO
0
k = A =
L.
(0
3 fe x ion A x 10n 3
Amount of Amount of Defined mass C M
(d
L. g (0
No. React! on So 1 vent Addend (D E
re act ant ad den d act I on 1 aw 0. E
>10 O -H
i k n n 0
-4 / 12\
.61 1- 2- 4-Cl3C6H 3 + N 2 8 ~> CT/NM 9* A = 1.20; B= 0.049 k AB 15 5.80 *
0.71 0.049 20 1.23 -3 17 ~1D
( continued) -3
0.82 0.043 20 1.07
1.15 20 1.00 -3
A- 0 -3 CO
CT/NM 7* 20 2.47
CT/NM ^ -0 20 2.76 -3
13
CO
Tetra-substituted benzene
( 6)
2.4,MCH 3 ) 3 C6H 2CH 2S0 3~+HN0 3 > M + BMol *= 37. 4; A= 0.29 dL/dt*0 0 1.09 -4 *
.62 ^
0 1.60 -4
80 ~CH -(CHJ *CaH N0 0 + H 00 39 ' 4 027
3233622 39.4 0.17 0 7.26 -3
V
Oi
Ob
SOLVENTS
CT/NM 9* 9 vol CC1 4 + 1 VOl CH 3N0 2
CT/NM 7* 7 VOl CC1 4 + 3 VOl CH^O a
CT/NM 5* 1 vol CC1 4 + 1 vol CHgNOg
ADDENDS
TEAP* Tetra ethyl ammonium pi crate
TEAHS* Tetra ethyl ammonium hydrogen sulfate
TEAN* Tetra ethyl ammonium nitrate
COMMENTS
Reaction. (.16) Pseudo first order rate constants measured by ciprocal of rate constant increases more rapidly. Reciprocal
( 9) asnitric acid in excess. Concentrations of benzene listed of zero order rate constant linear with respect to [H 2OJ over
by (9 ) not true concentrations but refer to optical densities. range studied. Initial concentration or H gO used rather than
In acetic acid at concentrations of nitric apid <12 mixed average. (.19) Pseudo zero order over entire course
order observed by ( 14) with initial reaction being pseudo in contrast to (. 16) . (.21) In CH 0COOH
3
rate law pseudo
zero order tending to first order in latter stages. Zero first order only when sufficient HM0 2 present initially.
order only at high nitric acid concentrations where large Side reaction leading to darK colored products making up at
addition of HN0 2 necessary to depress rate to measurable least 30%of yield cause autocatalyslsby the HNO g produced.
Co
value. HNO shown by ( 14) to have no effect on reaction order. Order with respect to HN0 2 varies with concentration of HN0 3
In CH gN0 2 linearcatalysisbyH 280 4 onlywhen [H 2SoJ>[HN0 2]. going from 0.65 when [HNO3] = 3.0 to 0.2 when [HNO g] = 6.0.
(.17) Active nitrating species considered by ( 11) to be In H S0 4 pseudo first order as HNO g in excess. Values of
3
N 0 which is involved In the following rapid equilibria: concentration of CH_OC RH K listed by ( 9 ) are not actually
O DO
2 5
HNO^ concentrations but functions of optical density. (.22)
Bz 20 + N 20 6 4=> 2BzN0 3; BzOH + N^^^T?BzNO g +
cata (.24) (.25) Second order rate constants calculated from
Bz 0 + HNO ^n? BzNO 3 + BzOH. First equilibrium is
pseudo first order initial rate constants dividing by en
lyzed by acid. Only in extremely pure Bz gO Is this equilibrium
concentration of N 20 5. At latter stages reaction shows auto-
slower than the rate of nitration. Under these conditions
catalysis by HN0 3 produced. Selected data, (.27) Se
nitration is so rapid that even the BzO g is nitrated. In a
(.18) Pseudo lected data from large amount by ( 13). Relatively small de
mixture rate is comparable to rate usingBzNO g.
pression of rate constants by N0 g" considered to be caused
zero order over entire course in contrast to (. 16). In CH gN0 2
by canceling of major effect by a large positive salt effect.
linear catalysis by H 2S0 4 only when [H 2S0 4]>[HN0 21 Recipro
( 6) observe initial rate to tend toward zero order followed
cal of zero order rate constant linear with respect to
by a limiting first order reaction. Addition of NaN0 3 de-
[HNoJ^ up to [iiWO ] = 0.08. At higher concentrations re-
!c 2
COMMENTS (continued)
presses both zero and first order rate constants to the same vent. (.37)(.38) Second order rate constants calculated
extent. Addition of NaC10 4 increases first order rate constant from initial pseudo first order constants by dividing by
more than it Increases zero order constant. (.28) Pseudo concentration of A which was in excess. At latter stages
first order as HN0 30 in excess. Values of concentrations of reaction shows autocatalysis by HNO g produced. (.39) Rate
C H GN listed by ( 9 ) are not actual concentrations but constants are in seconds converted from original minutes.
functions of optical density. (.29) Rate constants (.40)' Selected data. Rate constants converted to seconds
converted to seconds from original minutes. (.30) Addi from original minutes. (41) Rate constants converted CO
tion of water tremendously increases the inhibiting effect to seconds from original minutes of ( 19). In CH o0COOH ( 7)
of HNO g and changes it from a power effect in anhydrous observed first order dependenceuponHNO g up to [HN0 3] = 5.0
media, to a | power of [HNOj. (.31) Lack: of any but some inhibiting effect of HN0 2 observed at [HNO^ = 10.0.
measurable isotope effect shows that the rate determining The linear dependence of the calculated second order constants
step is no t the removal o f hydrogen. (.32) (.33) (.34) Rate upon [HNO^ from 1.4-5.8 considered to be due to a partial
constants pseudo first order as HNO 3 in excess. Concentra- balancing of strong effects. (.42) In CHgCOOH ( 2)
tlons of C 6 H 5 F listed by ( 9) are not actual concentrations deduce dependence of pseudo first order rate constant feupon
but functions of optical density. Selected data of ( 14) who [N 00
24
0 ] (fe. + fc 0K/[NO "]) where fe0*
1 and [NO 3~] as k = [N 24293
observe slight decrease in calculated first order constants is rate constant for nltrosation by N g0 4 andfe fornitrosa-
with Increase in initial concentration of C 6 H o F. (.35) tion by NO*. Nitrosation is assumed to be followed by the
Slight decrease in calculated first order constants observed + HN0 0. fe 0 determined
rapid reaction ArNO + HNO n3 >ArN0 0222
with Increase in initial con c en tr at ion of A. (.36) Rate from intercept of graph fc g = 1.3 * 10" 2 . A lower limit for
lawlszero order over entire course of reaction in contrast k 3 estimated from graph and upper limit for:
to (.16) which is mixed first and second order and (.32)-(.35) K = 1.9 x 10" 3 = [NO "] [NO*]/ [N.O 1
6 A *
which approach first order over entire course In this sol- lower limit =0.13. At = 5.94 the rate law of
COMMENTS (continued)
( 7 ), fc tA + fcA[HNO al is not valid at [HNO^ =0. In absence reaction course is found for this solvent. (.51) (.52)
of HN0 2 reaction is nearly zero order with respect to A, At (.53) Second order rate constants calculated from initial
5
in the range 6-9 M/l the kinetics are complicated pseudo first order constants.by dividing by concentration
having fractional non-constant reaction orders. At [HNOJ = of A. At latter stages reaction shows autocatalysis by HNO
9-10 simple orders are again observed if [HNO^ is not too formed. (.55) Initial rate of reaction tends to zero
large. Above [HNoJ = ID M/l the reaction is too fast to order. This is followed by a limiting first order reaction.
measure. (.43) Second order rate constants calculated Addition of NaN0 03 depresses both first and second order
from initial pseudo first order constants by dividing by rate constants to the same extent. Addition of NaC10 4 In CO
the concentration of A. At latter stages reaction shows creases first order rate constant much more than it increases
autocatalysis by HNC> 3 formed. (.44) Rate constants the zero order constant. (.56) Selected data. Rate
converted to seconds from original minutes. (.45) Rate constants in all H 2S0 4 media given by:
constants in H-O-H SO calculated by combining relative rates k = {k l [HS0 4~] + fe 2 [H 2 S0 4] + * 3 [H 8 8 807~] > Q
of ( 5) with rate constants for (.30) of ( 4) and ( 19 ). where Q= [NO^ / [HNO J = {l + [OH,*] [HS0 4~] 2/33[H 280 4] 2}~ *
(.47) (.49) Second order rate constants calculated from at 90C. 1D 6^ 1 = 5.8; 10 6 fe 2 = 6.2; 10 6 ^ = 9.3. Valueoffeg
Cfc
is in doubt as [HS 0 "] in oleum is uncertain. In excess
initial pseudo first order constants by dividing by concen 2 7
tration of A. At latter stages reaction shows autOGatalysis 90 , Q approaches 1. Rate constants converted to seconds
3
(.90) Reciprocal of rate constant from original minutes. (.57) (.58) Rate constants con
by* HNO 3 formed.
verted to seconds from original minutes. (.59) Selected
linear with respect to [HNO^r only up to [HNO^] = 0.08.
data. (.60) In CHgN0 2 good first order rate through
At higher concentrations the reciprocal of the rate constant
increasesmore rapidly. Excellent first order behavior over 97% reaction in contrast to zero order in this solvent for
(. 16) (. 18) and (. 19). (.61) Second order rate constants
97% reaction in CH 3NO o2 observed by ( 14). This is in contrast
calculated by dividing initial pseudo first order constants
to (.16) (.18) and (.19) where zero order behavior over the
COMMENTS (continued)
by concentration of A At latter stages the reaction shows and zero order rate constants to the same extent. Addition
autocatalysls by HNO formed. (.62) Initial rate of of NaClO^ Increases the first order rate constant much more
reaction tends to zero order. This Is followed by a limiting than It increases the zero order constant,
first order reaction. Addition of NaNO g depresses both first
LITERATURE
(*) G.M. Bennett, J. C. D. Brand, D.M. James, T. G. Saunders, G. Williams, CSL 1947, 474. ( 2) E.L. Blacfcall,
E. D. Hughes, C.K. Ingold, CSL 1952, 28. ( 3) T. G. Bonner, F. Bowyer, a Williams, CSL 1952, 3274. ( 4) T. G. Bonner,
F. Bowyer, & Williams, CSL 1953, 2650. ( 5) T. a Bonner, M.E. James, AM. Lowen, G. Williams, SAT 1949, 163, 955.
<>
( 6) C. A Bun ton, E. A Halevl, CSL 1952, 4917. ( 7) C. A Bunton, E. D. Hughes, C.K. Ingold, D.I.H. Jacobs, M. H. Jones,
O.K. Mlnkoff, R.I. Reed, CSL 1950, 2628. (8) H, Conn, E. D. Hughes, M.H. Jones, M. G. Peeling, HAT 1952, 169, 291.
( 9) N. C. Deno, R. Stein, ACS 1956, 78, 578. ( 10) R.J. Glllesple, D. G. Norton, GSL 1953, 971. oi
( ll) V. Gold, E.D. Hughes, C.K. Ingold, CSL 1950, 2467. ( 12) V. Gold, E.D. Hugies, C.K. Ingold, aH. Williams,
CSL 1950, 2452. ( 18) E. & Halberstadt, E. D. Hughes, C. K. Ingold, CSL 1950, 2441. ( 14) E. D. Hughes, C.K. Ingold,
R.I. Reed, CSL 1950, 2400. ( 1B) C.K. Ingold, A Lapworth, E. Rothsteln, D. Ward, CSL 1931, 1969. ( 16) AM. Lowen,
M. A Murray, 0. Williams, CSL 1950, 3318. ( 17 ) L. Melander, Acta. Chen. Scand. 1949, 3, 95. ( 18) L. Melander,
Arkiv. Ke*i. 1950, 2, 211. ( 19) F.H. Westhelmer, M.S. Kharasch, ACS 1946, 68, 1871. C 30 ) F.H. Westhelmer,
E. Segel, R. Schramm, ACS 1947, 69, 773. ( 21) G. Williams, AM. Lowen, CSL 1950, 3312.
Note: For compounds Involving more than one aromatic ring, it is understood that the substitution
take pi ace in the ri ng wri tten I ast. The posi tion of subst i tut ion in the product, if given, is des! g-
nated by a position number after the arrow counted in the same order as in the reactant.
JC
H 03 k = A =
D) 09 9 o>
C A x ion oL.
O
cd erf k. fe x ion CO
C Amount of E 3 3
L. 4-*
4) H c
No. Reacti on Addend CO
pH c s c d
0) 0 U E u
reactant C
0
+
i 0 O. fe A*
o E n n I
c c d
o t-
.1 0C ttH N * >
H + 4-CH 364*
CH,COCH 0CONHC 60 H 2 10 3A=2; Buffers 6.4 feAB 15 1.13 0 * ()
9
10 4B=2 6.7 15 2.67 0
7.0 15 5.53 0
10 3A=2J / 5\
.3 CH COCH CONHC H + 4-HS0 3C H4N + > H 2 Buffers 5.62 feAB 15 3.91 0 *
10 4B= 2 6.12 15 2.32 +1
-1 / 5\
1, 8- (HO) 3C6H 4 + 4-CH 3C6H4N a+ > H 20 10 3A=2; Buffers 6.0 teAB 15 4.40 *
.5
10 4B=2 6.4 15 1.26 0
6.8 15 3,83 0
.6 1, 5- (HO) 2C6H4 + 2-CH 3OC6H4N 2~*" > H 20 10 3A= 2; Buffers 5.82 feAB 15 1.57 -1 * ( 8)
10 4B = 2 6.25 15 6.12 -1
6.66 15 2.22 0
6.88 15 4.47 0
.7 1,5- (HO) C H + 4^CH OC H N + > H 20 10 3A= 2; Buffers 6.58 feAB 15 4.55 -1 * ( 5) CO
o 4 3642
104B=2 6.80 15 9.92 -1
7.00 15 2.08 0
I
.8 1* 3- (HO) CH + 4-HSO C H N "*~ > H 80 10 4A= 1-5 Buffers 0.24 4.50 feAB 15 1.97 0 * (*)
* O 4 3642
10 3A = 2; 5.0 15 4.90 0 * ( 8)
10*6 = 2 5.2 15 8.80 0 0
10 4A= 1-5 0.24 5.27 15 1.35 4-1 (*)
10 3A= 2; 5.4 15 1.52 +1 ( B)
10 4B= 2
.9 4-HOC H 80 0Na + 4-H80 C H N/ > H 2 10 4 A = 1-5 Buffers 0.24 8.17 feAB 15 1.1 -1 *
643 3642 Ci
9.15 15 5.3 -1
Mono-substituted napthalene
09 to fe = vi =
CD L.
C 9 > 9
-M 3 -in^ 4r\ft L.
O - KJLO *
v 1LJ ^JO xv 3Q V)
C Amount of U E 3
O .f
No. Reaction o c c Of
Addend m pH 0 O f w
react ant E c
o o t E *"
CD O fe A O
c ^ 0 K- n n 0
o _j
Q
Di-substituted napthalenes
.18 l-HO-3-HS0 0C in H + 4-C1C H N * > (2) ^5& (4) ^25$ H 20 JD 5A= 5; Phosphate 0.25 6.35 feAB 10 1.66 +3 (6)
3 1U 6 o 4 <e
1D 5B= 1 buffers
.13 1-HO-3-HSO C H -3-D 4- 4-C1C H N + > H 20 1D 5A=5; Phosphate 0.25 6.35 feAB ID 5.35 +2 (6)
3 10 5 o * U
10 5B- 1 buffers
> (2) ^80%, (4) ^30%
.14 l-OH-4-NaS0 3C 10 H6 -r C6H 6N 2+ > (2) H 2Q 10 4A= 1-6; Buffers 0.24 5.27 feAB 15 5.9 -1 (4)
*
10 4B= 1-5 5.80 2. ID 0
.15 l-OH-4r-Na80,C 1AHa + p-CH C H N 0+ > (2) H 20 10 4A= 1-5; Buffers 0.24 feAB 15 (4)
3 J.U O 9 Q 4 & 6. 3D 1.58 0 *
10 4B- 1-5 6.73 15 4.70 0
16 l-HO-4-HS0 3C 10 H6 + ^CH 3OC6H 4N 2+ > (2) H 2Q 10 3A= 1; Buffers + .005 5.7 feAB ID 4.6 -2 (18)
10B= 1 KC1 .01 5.7 ID 4.5 -2
.02 5.7 ID 4.6 -2
.05 5,7 ID 3.7 -2
.16 l-HO-4-HS0 0C, AH 4 a-CH _OC H N * > (2) ( continued) H 2 1D 3 A= 1; Buffers 4 .ID 5.7 kAB ID 3.2 -2 ( 18)
3 1O o 6 4 * -2
1D 5B= 1 KC1 .25 5.7 ID 2.8
10 4A= 5- ID; .24 5.80 15 1.37 -1 * (*)
1D 4B= 5 .24 6.30 15 5.09 -1
.24 6.73 15 1.22 0
.24 7.08 15 2.64 0
.24 5.80 25 3.28 -1 15 3 3D
.24 6.30 25 1.28 0
.24 6.73 25 3.08 0 16 2 12
'5.7 t la)
.17 H 4 4-CH DC H N + > (2) H 20 10 3 A= 1; Buffers 4 .005 *AB 3D 7.2 0
1-HO-4^HSO C
3 10 0 3642 ID 0
10 5B= 1 KC1 .01 5.7 7.4
.02 5.7 ID 8.0 0
10 8.1 0 CO
.05 5.7
. 10 5.7 3D 8.9 0
.25 5.7 10 9.8 0
4.50 25 4.45 0 15 4 11
.21 1-HO-5-H NSO C H 4 4-CH C H N + > (2) H 0 10 3A = 2; Buffers 6.4 k AB 15 1.33 0 * (")
2 2 10 6 3642 2
10 *B = 2 6.7 15 2.53 0
7.0 15 4.26 0
December, 1938
National Bureau of Standards - National Research Council
Homogeneous Reaction Kinetics
312.455
xv CO o
k - A =
o> W 9 i_ (D
4^ c ti of D fe x ion A x I0n on L.
C 9 E -H + 3
4>
Amount of L. Of c
No. Reaction > Addend -H T3 C i. S
m PH C 0 >
o td
C E i_
o reactant . .+- i- A E <D
CO o fe n 0 -H
<+- 0 9 n 0
c 0 CD 1
0 Lj
o
4-3 ( 10)
.25 8-HO-6-HSO C H 4- 3-CH.OC H N_+ > ( D H 20 10 SA= l; Buffers 0.25 4.61 k AB ao 1.20 *
3 111 O 9O 4 *
10 5B = 1
4-1 * ( 10 )
.26 3-HO-6-HSO C H + 4-CH OC H N/ > ( D H 0 10 2A= 1; Buffers 0.25 6.34 feAB ao 3.35
3 10 6 3642
10 BB = 1
4-1 / I2v
.27 3-HO-6-HSO C H 4- 4-HSO C_ H N + ( D HO 10 5 A= 1; Buffers 0.005 7.0 k AB 10 4.8 *
3 10 6 3642 4-1
10 5B = 1 0.01 7.0 10 5.0
0.02 7.0 10 5.1 4-1
10 5.7 4-1
0.05 7.0
10 6.3 4-1
0. 10 7.0
ID 6.3 4-1
0.25 7.0
.c k = A =
ro 0 0
c i. ^ x 10n m L.
0> |I 3 fe x I0n +j D
Amount of +* c +>
c L.
No. Reaction 0) Addend M PH d S o cd
ff)
-a ^ L_ E k.
_ react ant o o 0 E
0 O .f a. 0 Hc
CO E ** n n 0
*- 2 f _i
C to o
0 o
.35 ^ 2^HS0 3C 10H 6 + C 6H 8N 2+-(l) 10 8A= 1; 10 5B= 1 Buffers 0.25 feAB 2.24 ( 10)
H2 5.60 30 0 *
.36 8-Ml --fl-Ha) iC 10H 6 + 3.CH,CAH i+ ->(tt 2 10 3A= 1; 10 5B= 1 Buffers 0.25 5.60 feAB 30 8.5 -1 * ( w)
.37 a-NH 2-6-HS0 3C 10H 6 + 4-CH 3C6H4N 2+ -> ( 1) H 20 1D 3 A= 1; 10 BB= 1 Buffers 0.005 5.70 feAB 10 2.55 -1 ()
0.01 5.69 10 2.35 -1
0.02 5.67 10 2.19 -1
0.05 5.62 10 1.94 -1
0.10 5.58 10 1.66 -1
0.25 5.53 10 1.59 -1
10 4A= 1-100; 0.25 3.22 -1 (13)
5.09 20
-I (10) CO
10 5B = 1 0.25 5.60 ao 3.3 *
-1 (13) S
0.25 7.18 ao 3.84 12
,42 8-NH -6-HSO aC._H, + 4-HSO C H N/ > (1) H 0 10 5A= 1; 10 5B= 1 Buffers 0.005 5.72 feAB 10 6.81 +1
(9)
9 91UO 3 O 4 <6
0.01 5.71 ID 6.74 4-1
0.02 5.70 10 6.8 1 4-1
0.05 5.67 10 6.67 4-1
0.10 5.63 10 6.85 4-1
0.25 5.60 10 6.87 4-1
0.25 5.60 ao 1.05 4-2 7 * (
.60 -OH-6,8-(HSO g ) 2C loH4-l-D + 4-NOgC^N^ > (1) H 2 1Q4A= l;10 5B= 1 Buffers 6.65 feAB 10 3.24 +2 (")
.61 2-OH-6,8-(HSOj C, H. -H 3-C1C H N 4" > (1) 10 3A=2J 10 5B= 1 Buffers 7.28 feAB 10 1.07 +1 (")
3 2 1O 5 O 4 A V
.62 2-OH-6,8-(HSO ) C H -1-D + 5-C1C H N + > (1) H 3 10 3A= 2; 10 5B= 1 Buffers 7.28 feAB 10 1.95 0 (")
o A 1O 4 642
.63 2-OH-6,8-(HSO g) 2C loH 5 + 4-ClC^N^ * (1) H20 10 3A = 2-1; Buffers 6.69 feAB 10 6.2 -1 (")
10 5B = 1
10 4A = &-20 6.85 10 1.54 0
Base catalyst [Base]
C 0H 5N .0234 6.66 feAB 10 6.03 0
.0467 6.64 10 1.10 +1 CO
.0931 6.63 10 2.24 +1
.140 6.62 10 2.95 +1
.232 6.60 10 4.68 +1
.463 6.60 10 8.01 +1
.687 6.54 10 1.02 +2
.911 6.51 10 1.15 +2
2-CHC H N .0215 7.16 10 4.79 0
304
.0897 7.31 10 1.29 +1
.221 7.25 10 2.82 +1
.433 7.18 10 4.37 +1
3-CH C H N .0228 7.14 10 8.32 0
304
.0914 7.14 10 2.57 +1
,225 7.08 10 5.50 +1
.441 6.99 10 8.25 +1
4-CH CRN .0217 7.25 10 1.10 +1
354 4-1
.0897 7.39 10 3.47
.222 7.34 10 7.41 +1
.64 2-OH-6,8-(NaSO ) C H + 4-BrC H N + > (1) HO 104 B= 1-5; Buffers 0.24 5.80 feAB 15 9.40 -2 * (*)
a lu o t> 4 <&
A\E 6.73 15 6.00 -1
Heterocycllc aromatic CO
.65 NHCH-CHN-CH + 4-HSO C H N * >4-HSO C H ^TClNCH'CHNH + H+ H 20 10 4A= 1-10; Buffers 7.10 feAB 25 3.0 -1 * ( 8)
o O 4 2 J o 4 2
10 5B = 1-5 8.15 25 1.20 0
9.15 25 9.1 0
10.0 25 3.52 -!
11.0 25 4.69 ^
.66 C H CH-CHNH + 4-NO C H N o+ >C H NHCH'C-N C H -4-N0 0 + H+ H 20 104A = 1- 10; Buffers 4-6 feAB 0 2.3 0 ( l)
64 2642 64 2 4 2
10 5 B = 2-5 6.7 Q 3.1 0
(indole)
7.6 0 3.9 0
8.6 0 5.2 0
9.2 0 4.5 0
^
4.1 <D
fe =
CO 0)
O) L. ikO x 1Q L.
CO 9 0)
c D 3
of <d -H
*-
c Amount of 0
05 c cd
React ion > Addend pH -o c L. c
No. E
m 0 0 to Q>
0 reactant c Q. E -M
CO E fe 0
o n 0
H- 0 O _J
c j_
0 03
0 O
1. 1 + ( 5)
.74 H 20 10 3 A=2; 10 4B=2 Buffers 4.53 kAB 15 1.38 0 *
5.06 15 4.47 0
(3-methy l-1-pheny 1- 5-pyrazol one)
5.31 15 8.33 0
4* ( 6)
.75 H 20 10 3 A=2;10 4B=2 Buffers 5,2 feAB 15 1.90 0 *
5.4 15 3.33 0
(3-methy l-1-pheny 1- 5-pyrazol one)
5.6 15 5.55 0
COMMENTS
Genered. In mostof the coupling reactions listed, pseudo first order rate constants were determined with dlazonium
ion in smaller amount. Second order rate constants were calculated by dividing pseudo first order constants by analytical o
concentration of reactant in excess. In some cases authors also divided pseudo first order constants by calculated concen
tration of supposed reactive species. Such values have not been tabulated except where so stated under comments. Diazo
coupling reactions are listed in order of the compound undergoing coupling, substituted benzene derivatives being listed
first foilowed by mono-substituted napthalene, then di- and tri-substituted napthalene derivatives. These are followed by
heterocyclic substances. In each group the compound with OH precedes NH2 , N0 g , HS0 3~, Cl~, Br~, and I . Compounds with
substltuents in the 1-position precede, 2, 3, 4 etc. The diazonium ions are also arranged in a corresponding order.
Literature. (4) Units of rate constants converted to seconds from original minutes. A to B ratio varied from _5 to
5. Plot of log of rate constant vs. pH observed to be linear with slope of unity. ( 5) Units converted to seconds
from original minutes. Amperometric method used. Buffers used were Clark and Luba. Plot of log of rate constant vs. pH
linear but slope varied from 0.6 to 1.3. ( 5) points out that similar plotby ( 4) had slope 0.9 not unity. { ) Units
converted to seconds from original minutes. Concentrations of reactants not stated by authors. pH dependence concluded to
Indicate coupling involves diazonium Ion with free amine.
COMMENTS (continued)
Reaction. (.6) Rate constant converted to seconds from corrected for side reaction. Yield of product of coupling
original minutes. Reaction followed potentlometrlcally. Au 75.5$. Approximate value for activation energy calculated
thors calculate rate constants for paths Involving HOC H (T by editor. (.38) Rate constant corrected for side reac
O 4
and OC H 0" ions. (.9)
Calculated second order rate tion. Yield of product of coupling 89.8$.
0 4 (.39) Rate
constants decreased with progress of reaction in this alka constant corrected for side reaction. Yield of product of
line medium. Values approximate. (.11) Authors studied coupling 82.8$. (.40) Rate constant corrected for side
in detail influence of temperature, base catalysis and reac reaction. Yield of coupled product 73.7$. (.41) Rate
CO
tion medium upon ortho and para coupling. (.22) Rate constant corrected for side reaction. Yield of coupled pro
constant corrected for side reaction and calculated in terms duct 68.1$. (.42) Rate constant of ( 10 ) corrected for
i
of naptholate ion asreactant. Yield 98.8$. (.23) Rate side reaction. Yield of coupled product 67.3$. Approximate
constant corrected for side reaction and calculated in terms value for activation energy calculated by editor. (.43)
of naptholate ion as reactant. Yield of product of coupling Kt
Rate constant corrected for side reaction. Yield of coupled CO
82.256. (.at) Rate constant at 20C by ( 10 ) corrected product 84.4$. (.44) Rate constant corrected for side s
for side reaction and calculated in terms of naptholate ion reaction. Yield of coupled product 89.6$. (.45) Ac
as reactant. Yield69.5$. (.25) Rate constant corrected tivation energy and frequency factor of doubtful accuracy
for side reaction and calculated in terms of naptholate ion as based on only two values ten degrees apart. ( ) cor
as reactant. Yield 88.1$. (.26) Rate constant corrected rected rate constant for side reactions. Yield of coupled
for side reaction and calculated In terms of naptholate ion product 71$. (.65) Authors show reactive species is
as reactant. Yield92.i$. (.28) Rate constant corrected probably anlon of A since plot of Its concentration vs. pH
for side reaction and calculated In terms of naptholate ion has same shape as plot of rate constant vs. pH. (.68)
as reactant. Yield89.2$. (.29) Rate constant corrected Rate constant corrected for simultaneous zero order de
for side reaction and calculated in terms of naptholate Ion as composition of B with 109 fe0 = 0.6, 9.0, 20.0, 5.0, 1.0 and
reactant. Yield 89.2$. (.33) (.34) Units converted to 25.Oat thepH's8.5, 8.65, 9.0, 9.15, 9.60 and 10.1 respect
seconds from assumed minutes. (.35) Rate constant cor ively. Rate constant also corrected for consecutive reaction
rected for side reaction. Yield of product of coupling 89$. (.69) between B and L. (.69) A consecutive reaction to
(.36) Rate constant corrected for side reaction. Yield of (.68) products not determined. Rate constant gives order of
product of coupling 88$. (.37) Rate constant of ( 110 ) magnitude only.
LITERATURE
C 1) J.H. Binks, J.H. Ridd, CSL 1957, 2398. ( 2) R,D. Brovm, B.A.W. Coller, M.L. Heffernan, CSL 1958, 1776, Co
( 3) R.D. Brown, H. C. Duffin, J.C. Maynard, J.H. Ridd, CSL 1953, 3937. ( 4) J.B. Conant, W.D. Peterson, ACS 1930,
|
52, 1220. ( 5) R.M. Elofson, R.L. Edsberg, P. A. Meckerly, J. Slectrochem. Soc. 1950, 97, 166. () R. Erast,
O.A. Stamm, H. Zollinger, HCA 1958, 41, 2274. (7) 0, A. Starara, H. Zollinger, HCA 1957, 40, 1955. (8) R. Wistor,
Co
P.D. Bartlett, ACS 1941, 63, 413. (9) H. Zollinger, HCA 1953, 36, 1723. ( 10 ) H. Zollinger, HCA 1953, 36, 1730. g
( lx) H. Zollinger, HCA 1955, 38, 1597, 1617, 1623. ( 12) H. Zollinger, HCA 1956, 39, 1600. ( 13 ) H. Zollinger,
V) /fe - A =
m s 4>
**- L. CO u
ed s 3 k x ion X x J0n
E H
Amount of ^ Of C
-0 C w. g
No. Reaction Sol vent Addend "c 4> 0 E J
c o O
re act ant -M Q. 1
*- 0
fe n A n 0
io i 0 05 i
h- 3
Q
.2
V. * V. - fPt * V w. A= 0.1-0.5; . ,= ^ bn- (*,/*>*] "/-*. M/ A( 1 -H <?M ) * (4> C/)
B = 0. 1-0.3 40 -5feQ 1.55 7.5
40 fe t 1.68 -6
40 fe g 4.63 -3
40 q 3.89 +3
.9 MCH 3) 2CflH4 + H a80 4 -* (CH 3) 8C6H 8 a> 3H + H 80 w2 A = 0. 1-0.5; fe AB;fe= fel [M+(Vfe, )1-<"-jVKi + *> *
(*)
B = 0. 1-0.3 40 fe 2 8.79 -3
C continued)
40 q 1.61 +3
.10 .1 ,-CH 3C6H4N0 8 + H 8 804 -> B + M A=0.2jM=0.78 feA/M(M + [HSO 4"]) 70 6.4 -7 * ()
" 1.05 - 70 7 t)p -7
1-CH -2- SO H-4-NO C H + H 0 CO
3 3 2632 70 8.9 -7
" 1.33 R
" 1.78 70 8.3 -7
M 2.24 70 1.08 -6
" 1.14 80 2,39 -6
" 1.36 80 2.56 -6
" 1.78 80 2.78 -6
11 2.24 80 3.20 -6
" 2.73 80 3.33 -6
CO
A=0. 1-0. 2; M= 1.4-5.5 96 1.9 -5 CTi
Ob
0.4 1.38 96 1.5 -5 27
0.2 2.17 NaH80 4 0.2-1.0 96 2.00 -5
1.47 0.9-2.6 96 1.66 -5
" 1.06 0 -0.9 96 1.84 -5
ti n 2.0 96 1.66 -5
n n 2.8 96 1.58 -5
B+S0 3 A=0.2J [soj =0 .44 * A[80 a] 13 2.36 -5
1. 1 13 3.1 -5
" 2.2 13 4.0 -5
" 0.2-0.8 25 8.4 -5
1.2 25 9.5 -5
" 0.5-1.5 40 4.2 -4 18 2 9
A < 0.1 [SO^ JtSOg = 4 . 1 feA 20 1.0 -4 * ( a)
7.4 S3 2.3 -4
.10 .1 ^ CH 3CeH 4N0 2 * H 2a) 4 * (continued) B + S0 3 A < 0.1 [S0 3] S0 3 = 11.4 feA20 -4 * (')
4.4
30. 1 30 1.2 -3 19.5 6 10
4-3D fc'AttfloJ/B) 1' 8
1 2 3.0 -3
C6H 5N0 2 A= 0. 1-0.3 M + (fc./fcJ 3]~ M/A(1 * q!i ) * (*)
B = 0. 1-0,3 40 3.3 -6 ' 9.8 CO
40 fe t 3.5 -7
40 fc n 2.75 -3
2
40 <7 1.11 --3
CO
.11 ^~ GH 3C6H 4N(GH 3> 3+ + H 2S4 ~~^ B SO _j A < o.i [aOg] %80, = 4.1 *A 25 5.0 -3 13.2 2.6 7 * (")
o
11.5 25 9.0 -2
1-CH >--S0 30H-4-(CH_)
d O
JJ+C O H,J + H ^00
4-11 W A\ LL
X) 3]/B) 2' 2
25 3.5 0
Oi
Ob
.12 (*)
-CH 8C 6H4Cl + H aS0 4 >CH a-ClC6H 3 S0 3H + H 20 W2 A = 0.1-0.3 V3- fe 2fi/A(l * (^i ) *
"ID 7.4
B = 0.1-0.3 ko 1>?1 -5
40 * t 1.85 -6
40 *2 4.59 -3
40 q 3.36 +3
.13 *- cl 2C6H4 + H 2804 ^CWt80 .8 + H 2 C6H 0N2 A = 0.1-0.5; feAK>*= ^[M^ (* t/*>0) 31- V3-* 2P/A(1 -*- qM) * (*)
B = 0.1-0.3 40 *o 6 ' 7 -6 9.5
40 /3 t 9.2 -7
40 fe g 1.99 -3
40 g 2.36 +3
Q. rc
*.8
1 10
p
0
c *i
X
l 9
to
1 P s
to to H-
CO
3 O a,0
X 0
rc 3
+ o
s 8
1C
*ffi "a
o
+ +
s tc ffi
Mo "o
w
o O 09
a 'ao 0 w 0
a
Substi H*
o I 3
CD 10 to rt-
it9 10
** cr
c CO tz) >
ri- C*
h* II II li II
II 11 9 II II JJ" 0 0 O 0
0 0 0 0 5 1
d- T *r
T T T (D 0 O
S 0 0 0 ? ?
5 a w 5? w W
E
OJ fl! ea fi?
sr cr
P
M
(D N
3
(D 3
A 3
Q.
Amount of
addend
str *tr 30- 30-
Defined mass
30- 30*
,5 15 act! on 1 aw
.,!,,___ =lr<
II II II
3ET
Temperature
6 6 6 6 6 fe 6 6 _* 5 0 0 30-
*T 5" 5"
-Q 30- 30- _3r
(0 *+ + 10 H O + |o r ^o^ +
M- CJ1 H-^ *-* S*3 ^ r3 r3 "^ w <i M. H- c: H.k l_t CO *-* *o *
^ at> -N} CD O) M fO O O O H Q -*3 0 ioj*" X
2 K H* CO H* "**- O hA O> ^-
...
| 1 1 CO
31
+ 111 CD + + ' ' X -- fl i i ^ *^
W CP cn 4* w ^ OD <3 -3 O5 ^ *** <3> i__i O3 C
t 1 1
^ ^* ta
<
a I** CO J
* IM ag
30- C ar "*3 ^ 03 JO
M
10,
> ^
X
o + +
0
O s 9 'S
^ 3
O"
0 Comments
* *
3 Li terature
3 3 3
9S6T
Homogeneous Reaction Kinetics
312.462
k - >j =
ft x 10n " x i<
Amount of
No. React i on So 1 v en t Addend o c
reactant e o
c
._ -H
M- O
o cd
o
18 a- C io Hr NO a A = 0.1-0.5;
T*-
B = 0. 1-0.3 k 2.61 ^-5 8.4
40 6 2.98 -6
40 k2 8. 17 -3
CO
40 q 3.57 +3
COMMENTS
Reactions. (.2) (.3) Followed by turbldimetrlc method for original minutes of ( 2). (.5) Analytical method for
H 0 by ( 4). Rate dependent upon concentration of water as A with units converted to seconds from original minutes.
given by expression for k which holds for first 5 to 7% First order with respect to A as B in excess. Rate constant co
en
reaction only, and for [HgOl^O.015. feQ Is measured rate found to be proportional to the ratio [H a8a0 7l/[HgSoJ to Oi
constant for initial rate and the fe and & 2 terms are re the 2.4 power. [H 2 S 20? ] taken as equal to the S0 a added.
lated to the forward and reverse reactions. Simultaneous Temperature dependence studied from 0 to 40 C. (.6)
sulfonatlon of solvent given by (.4). (.4) Reaction (.7) Followed by a turbldlmetrie method for H 20. Expression
followed by turbidimetrlc method for H 20 by ( 4). See (.2) for dependence of rate upon H 0 valid for first 5 to 7% reac
(.3). Reaction using spectropho tome trie method In fuming tion and for [H o]<0.015. Measured rate constant for Initial
2
sulfuric observed by ( 2) to be pseudo first order with respect rate is k . Terms for forward and reverse reactions Involve
to A as B in excess. Rate constant found to be proportional k and k . For simultaneous sulfonation of solvent see (.4),
to first power of the ratio [H 2 S20 ?]/ [H 2 SoJ where [H 2S 20?] (.8) Comparison of sulfonation at hydrogen and tritium
was taken as equal to the SO 0 added. Rate constant calculated studied In both fuming sulfurlc and nitrobenzene as solvent.
in terms of total C H NO and CgHgNOgH*1" rather than true (.9) Followed by a turbldimetrlc method for H^O. Expression
C H-NO concentration. Units converted to seconds from for dependence of rate upon H 80 valid for first 5 to 7% reac-
CO
Pi
rH
rH S SCD
CD
40
g
4-H
Pi
rH
d FH
CD
0
CD
S T3
0
o Pi d 8*
CD 0 6
rH
40 CD
Icd CQ CO
1 CD
Pi cd
4-H i\
d t- C9
0
8 ctoUnioratHS04 (.
(.12)
13)
(.14)
(.15)
aurvtecohdes.lavntihsnmg (.16) toiucglfotiensda.stlng
nagent
eand
sabase
miorfrom
a vdiasmeewinnt
of
ebase
rnsuch
iH
1ftis
3kQ)
for
and wvrnac-emsareartvsdesnest of
elgiiup
plot
to
rate
orc( fnlouavnonstcasnutnseiloavuntsed
Iitlmcbut
fc
and
uFor
sk^ co riefor
Is
1 oretaiuncoglreitmnddasl 5-7%
Meocinortfisarted
ncarate
(.17)
(.18) to for
f/^
wiociwesntderiensaorp.vntdeecth [Ha
o] coa0At
rate
and tlrn15.vhcdmeinesetrgations
o<0.IeTernwac-vfor
ris
40
N02
H5
by
O
C6
).
(
42) nrobindtshm.itodeanrilct
acrate
meired
TIn
Hg
for
used d 1 CD
valby
refor
| fe A
agircfeNet bvQ
otairto urbof
T(.4). sfiof
idseeoumlS0g
s] emialctasniokentenuns t
voeatnuris
o 0
S
CD S ricenand
ais
fe2
for
e[H
[fl
r]
For SO
i/ rnlstv.elmionnag l
to
S
eo0
tvtion
s
Pi
s
OH 0
40
a-
0
cd
PI i *? tH
C.
Br(
)
1930,
CSL
21004. trlasnd.oern,, HiC.n(*)
and,MeL.
ArUv.
1953,
Ke*i
6,
219.
J.
4-1 8 g CD
CO
oiOSL
lu1.
wN187
WisC.hStelF.J. 1949,, s., , es,
dm.a
aDDavibbs&
0 Pi 40 cd
CD 40
O
4H
Pi S
S
cJ
CD
rH
0
2n
1CD
d d
0
40
cd
Pi
CD w
O CQ
40 Oil
o O
4-H 40
CD
d
CD
CD 0 o
(continued)
COMMENTS 0
rH
Pi CO 40
CO 40
CO
CD
d
O)
0
CD a
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Homogeneous Reaction Kinetics
312.467
COMMENTS
Pseudo first order with respect to B as A In excess. Order with respect to catalyst,
A1C1 , not determined. Beyond 50$ reaction calculated rate constants decrease. Units In
seconds calculated from original minutes.
CO
CO
cs>
LITERATURE *
8.C.J. Ollvler, RTC 1914, 33, 146, 244.
Where there may be doubt about the position of the substitution, the H exchanged is printed in bold-face type.
CO
a
ro CO k =
c A =
^ _ OT l_
cti cd 3 -M
E k x 10 f\ 4 x ID C
Amount of Amount of
-o c S L.
No. 6 M React i on Sol vent Ad dend *
react an t addend c Q. o
Q. <* A" o
4- O A n n
o etf -J
3 Q
CO
CD
Saturated aliphatic Derivatives cn
01
OH~ ( 2)
.46 . 1 CH COCH + 3C10~ > (contJ HO A = 0.31; 0.034\ k AB 0 1.24 -3 *
o 3
10 3B = 1.5 cr 0.22 J
-5
3
25 2.49 19.7 cs-
Ac75 N n n n 0 2.26 -6
15 1.63 -5
25 5.27 -5 20.1
H 20 A = 0.1; CH 3 COO" 0. 147 feA 35 8.91 -7 * (")
B = 0.005 45 2.58 -6
55 7.05 -6 20.7
Ac 25 n n n n 35 1.54 -6
45 4.32 -6
55 1.12 -5 19.0
Ac50 n n n " 35 2.36 -6
45 6.40 -6
55 1.68 -5 19.4
Ac75 n n n 35 2.92 -6
45 7.66 -6
55 1.88 -5 18.5
.2 -6 (")
.47 CHJ30CH, (contj AC90 A= 0.1; CH,COO" 0.147 *A 35 2.82 *
33 o
+ Br *
B = 0.005 45 7.50 -6
54 1.97 -5 19.3
OH" -2
.48 .2 CH 3COCH 3 + 3BrO" > H 20 10 4 A = 7-8; 0.007-0.07 k A[OH~] 0 0,2 *
10 3B =1.5-5 10 1.60 -1 CO
CH C00~ 4- CHBr + 20H~
<Y)(7) K
3 3 18 3.12 -1 a
25 5.2 -1 13.4 3.5 9
CX)
* (6)
.49 .4 COCH 0 + I A = 0.27; U ) buffers ^I1/5MI
i 1
CH 332 H 20
10 3 B = l- H 20 55.5 25 8 -12
OH" -1
*i 25 2.5
H 0+ fc -5
fti 25 2.74
(&-20)10~ 3 -7 CO
(CH g) 3CCOO~ *1 25 4.08
(CH 8 ) gCCOOH (2- 3D) 10" 3 *1 25 7.3 -8
CHgCQO" (2-10) 10" 3 ^1 25 2.44 -7
CH gCOOH (4-100) 10"* *i 25 1.01 -7
CH OHCOO" U= 0.11 ^ 25 3.85 -8
2
CHgOHCOOH JJL* 0.11 fe l 25 3.25 -7
CH 2C1COO~ IJL = 0.2 *i 25 5.0 -9
CH 2C1COOH ^= 0.2 ft 25 1.27 -6
C H Cl 0~ /x= 0.11 k 25 7.56 -6
CH gCOO" * ( 8)( 88 )
H 2 A= 0.27; 0.02-0.21
0.02-0. 8[
(see coniments>)
10 3B = 2 CH.COOH
o
10 4A = 7-8 ;
OH" 0.007-0.035 fc A[OH"] 0 6.,9 -2 * CM7 )
.50 .4 CHJ30CH. + 310" > H 0
3 3 -1 ( )
10 3B = 1.5-5 10 1.60
CH 0COO" + CHI a + 20H~ -1
3 18 3.12
25 5.2 -1 13.4 3.5 9
.51 0COCH 0 + 2,4-Cl 2 CHN(C: OCR 3JC1 :6H 5ci 10 2B = 0.85 CHgClCOOH 0.0138 -aB<Vdt 50 7.85 -8 *
(')
o 4-
CH 33
1.5 0.0138 50 8.65 -8
>CH COCH Cl -H 2,4-Cl C H NHCOC H o
92 264 3 -7
3.0 0.0138 50 1.73
6.2 0.0138 50 3.08 -7
S3 9.5 0.0138 50 3. 17 -7
-7 CO
^ 15.7 0.0138 50 4.14 K
it s> 2 0.0072 50 9.84 -8
5.0 0.0072 50 1.69 -7
-7 CO
7.6 0.0072 50 2.06
15.1 0.0072 50 2.40 -7
.52 CH 3 COCH 3 + [(2,4, 6-Cl 3C H ) C1N] C'O W1 10 2B =3.4 CHgClCOOH 0.0072 -dB/dt 3D 2.11 -7 *
(8)
$ 5.5 0.0072 50 2.60 -7
C:Q CO
2 2
CH COCH 0C1 + [(2,4,6-Cl o C o HjHNj
o <& -7
^ 10.5 0.0072 90 3. 17 Cn
11 17.6 0.0072 50 3.25 -7 en
.54 (CH 3) g CCOCH 3 + Br 8 Ac75 A = 0* 1; B = 0.005 HC1 0.5 feA 25 2.34 -5 * (")
35 7.40 -5
45 2.02 -4 ao.3 1.8 K)
.56 (CH 3 ) 2CHCOCH(CH 3 ) 2 + Br 2 AC75 A=0. i; B=0.005 HC1 0.5 *A 35 2.02 -5 * (>
45 6.65 -5
55 1.99 -4 22.8 3 11
.57 (CH 3 ) 3 CCOCH 2CH 3 + Br 2 AC75 A=0.1; B= 0.005 HC1 0.5 fe A 25 9.0 -6 * {")
35 2.90 -5 CO
45 9.4 -5 21.8 9 10
.58 ( CH 3 ) 3CCOCH 2C 2H^Br 2 AC75 A=O.U B= 0.005 HG1 0.5 fcA 25 8.0 -6 * (17 }
35 2.56 -5
45 8.0 -5 21.3 3 10
.59 (CH 3 ) 3CCOCH(CH 3 ) 2 + Br 2 Ac75 A=0.1; B=0.005 HC1 0.5 feA 35 1.74 -6 * (") Kv
CO
45 5.98 -6
55 1.72 -5 22.7 2 10
.60 10 2A = 2-6 ( 6)
CH COCH 0G1 + I H 20 buffers JJL = 0.11 ^i Mi *
32 2
X = H 20 n fe i = 25 4.8 -9
OH~ n l = 25 2.0 +2
H 0* n < 3 -6
^ = 25
(CH 3) 3 CGOO~ n \ = 25 2.64 -4
GH 3COO~ n fe i = 25 1.87 -4
CH 2OHCOO~ if /e = 25 2.52 -5
CH 2C1COO~ JjL= 0.2 25 4.59 -6
.61 CH COCH Br + I U r\ ( 6)
H 2 buffers S.AX *
32 2 1 1
XA - H 20 JJL= 0. 11 *i = 25 9.7 -9
OH " fc = 25 9.3 +2
H 3"H " -5
fc = 25 6.32
(CH 3 ) 3 CCOO~ ti ^l = 25 1.85 -4
CH 3000~ it = 25 1.07 -4
CO
^i
CH 2OHGOO~ n k ~ 25 1.75 -5 c
hi " -6 T3
CH 2C1COO~ fJL = 0.2 25 2.97 XJ
c**i
C6H 2C1 3~ jji= 0.11 \ = 25 5.30 -3
CO
a
( 6) CO
.62 GH O_COCHC1 ,
+ Br H 20 buffers /JL= 0. 11 2> 1AX 1 *
X = H 20 n fe = 25 1.32 -8
OH~ *i = 25 4.5 +2
H 0+ ti k = 1.8 -7
25
I! *i = 25 1.34 -3
(CH 3) 3 CCOO~
CH gCOO~ n fei = 25 5.63 -4
CH 2C1COO~ /^ = 0.2 *1 = 25 2.08 -5
Ke to-Ketones
* ( 6)
.63 CH 3COCH 2CH 2COCH 3 + I g H 20 buffers Se lAX 1
JJL = 0.11
\ ~ 25 4.2 -11
H 0
OH" n te = 25 1.7 0
H 0* n fe = 25 2.52 -5
(CH 3) 3CCOO" n *i = 25 2.52 -6
CH 3COO~ N /e i = 25 1.43 -6
CH 2OHCOO~ n K - 25 2.94 -7
CH 2C1COO" fJ. = 0.2 ki = 25 2.5 -8
CH 3COOH /X = 0.11 ^1 = 25 6.3 -8
CH 2OHCOOH n k - 25 2.2 -7
/U= 0.2 k\= 26 9.7 -7
CHgClCOOH
.64
( 31)
CH 3COCH(CH 3)COCH 3 + Br g H 20 10 2A= 3.3; feA 21 5.8 -5
10 3B = 3 25 8.3 -5
35 2.3 -4 18 1.2 9
-3 (86)
.68 CH-CH EtlO A^ B^O.Ol feA 14 2.96 *
25 1.01 -2 19 8 11
II H
CH CHCOCH GOCF 0 + Br
\ / 23 2
8
-6 * (")
.69 . 13 CH j3 COC o H o + Br ; Ac 25 A=0. 1: B=0.005 HC1 0.5 feA 25 7. 12
35 2. 13 -5
-6 ( 16 }
.70 .14 CH3CO(w-C6H 4CH 3) + Br 2 AC75 A=0. 1; B = 0.005 HC1 0.5 *A 15 7.43 *
25 2.47 -5
35 7.41 -5 20.0 1.2 10
-6 ( 16)
.71 .15 CH aCO(m-C HNO A ) + Br AC75 A=0.1; B=0.005 HC1 0.5 hk 15 2.5 *
O O 4
25 8.2 -6
35 2.70 -5
45 7.96 -5 21.0 2.1 10
,72 .16 CH 3CO(^C6 H 4N0 2) + Br 8 Ac75 A=0. 1; B-0.005 HC1 0.5 /e A -6 ( 16)
15 3. 16 *
25 9.8 -6
35 3. 16 -5
45 9.5 -5 21.0 2.5 10
CO
,73 . 17 Ac75 A = 0. 1; B^ 0.005 HC1 0.5 k A 25 1.38 -5 ( 16)
CH CO(-CH F) + Br 2 *
35 4.36 -5
45 1.28 -4 20.7 2. 1 10
,74 . 18 CH 3 CO(-C fl H 4 F) + BT " Ac75 A=0. 1; B= 0.005 HC1 0.5 feA 25 1.49 -5 *
(16)
35 4.78 -5
45 1.36 -4 20.5 1.7 ID
Ac75 -6 (16) Oi
.75 .13 CH 3 CO(-C8H 4C1) + Br 2 A=0. 1; B= 0.005 HC1 0.5 ^A 15 3.58 *
25 1.22 -5
35 3.92 -5
45 1.15 -4 20.8 2.2 ID
-6 (16)
.76 CH 3CO(-C 6H 4C1) + Br 2 Ac75 A=0. 1; B=0.005 HC1 0.5 k A 15 4.7 *
25 1.52 -5
35 4.73 -5
45 1.40 -4 30.6 2.0 ID
-6 (16)
.77 .20 CH CO(m-C H Br) + Br s Ac75 A=0. 1; B=0.005 HC1 0.5 *A 15 3.63 *
25 1.23 -5
35 3.99 -5
45 1.17 -4 SO. 8 2.2 ID
.78 .21 CH 3CO(*>-C6H 4BD + Br 2 Ac75 A=0. 1; B = 0.005 HC1 0.5 4.83 -6 * (16)
kA 15
25 1.54 -5
35 4.74 -5
45 1.45 -4 20.4 1.4 10
-5 (16)
.80 .23 CH oaCO(-C O H 4 I) + Br & Ac75 A=0. 1; B=0.005 HC1 0.5 fcA 25 1.62 *
35 4.97 -5
45 1.47 -4 30.4 1.5 10
CO
-6 (14)
.81 .28 CH o CH A2COC O H O + Br A Ac75 A=0.1; B= 0*005 HC1 0.5 kA 25 9.0 *
35 2.94 -5
45 9.35 -5 22,1 1.4 11
n n H 6.65 -7 (16)
CH 8CO(f 0.147 kA 45 *
55 1.81 -6
65 4.72 -6 19.9 3 7
-6 ( 14)
.82 .30 Ac75 A = 0. 1; B=0.005 HC1 0.5 kA 25 6.01 *
202 65 2
35 2.03 -5
45 6.45 -5 22.0 8 10
M n N -7 (15)
CHgCOO" 0.147 kA 45 5.20 *
55 1.43 -6
65 3.62 -6 30.2 4 7
-6 (")
.83 .32 (CH 3 ) 2CHCOC6H 8 + Br 8 Ac75 A-0, 14 B = 0.005 HC1 0.5 .A 25 1.77 *
35 6.06 -6
45 1.92 -5 22. 1 2.9 JO
N n ( 1B)
CH 3COO~ 0.147 fcA 45 1.27 -7 *
55 3.70 -7
-7 CO
65 9.9 20.9 3 7
7. JO -6 * (")
.84 .34 n-C,H 7CH aCOC 0H 8 + Br 2 Ac75 A=O.U B=0.005 HC1 0.5 feA 25
-5 Cfe
35 2.36 3
45 7.30 -5 21.7 6 10 CO
n n n -7 ( 18)
CHgCOO" 0.147 teA 45 5.86
55 1.57 -6
65 3.99 -6 20.1 4 7
-6 ( 15) C7!
.85 .35 AC75 A=0. 1; B=0.005 HC1 0.5 feA 25 2.79 *
3 2 200 2 -6
35 9.34
45 2.89 -5 21.7 2.3 10
" n ft CH-COO" 0.147 *A 45 2.54 -7
o
55 7.07 -7
65 1.87 -6 20.5 3.2 7
-6 ( 14)
n~C 4H0 CH 2COC6H 5 -f Br 2 AC75 A=0. 1; B=0.005 HC1 0.5 *A 25 6.81 *
.86 .36
35 2.22 -5
45 6.86 -5 21.4 3.4 ID
Mono-carboxylic acids
-2 <")
CH 8COOH A = 2B = 0.025 NaBr 0.65 fcAB 25 1.58 *
.87 CH COON a + Br g
n 35 3. 18 -2 16 ~11
0.2 35 6.0 -2
Ac92
0.2 35 1.4 -1
Ac80
s
* Comments
* wo * *
1
^~w ^ w M L i terature
^ ^9 ^>
J8
^t
Homogeneous Reaction Kinetics
312.471 13
OJ k = X =
c 09
09 X o o
tf id 3
mn
ji x** 1U
a
CO v_
c E - 3
o> z Amount of Amount of c M
05
o c u S o 03
No. Reacti on So 1 vent Addend 0 0 E I-
J - c o E O
reactant addend 0_
E k yj O
Q. <H 4- O n n 0 it!
3 0 0* K -J
CO Q
.92 Oi 2CH 2CH 2C:0(?HCOOC 2H 5 + Br g H a 10 3A=3-7; B<A Acids + 0-0.1 fc A + Sfcj AX4 * (88) Oi
salts 0-0.3 IB k = 1.34 -3
xi = <*** 18 fcJL = 1.22 -1
18 *t =8.25 -2
La"1"1"1" -2
18 fc = 5.65
Zn* 4" 18 k = 2. 11 -2
Pb* + 18 ft = 1.07 -2
Mn+ + 18 fe* = 6.5 -3
Cd+ + 18 k =6 -3
Mg** 18 feA = 4. 3 -3
Ca+ + 18 k = 4. 1 -3
Ba"1"* fc = 1. 1 -3
18
H+ 18 /? =7. 1 -4
Be+ + 18 A5^=5 -4
.,-f+4- -4
JxL 18 i
yr -** -5
ii d 18 ^=5
K+ 18 ^=(0.0)
,92 bH 2CH 2CH 2C:otHCOOC 2H 8 + Br a R8 10 3 A= 3-7; B< A Acids + 0-0.1 K A ' ^<rS ^^j * ( 2B)
salts | rz
n\j nw.<_>
X1 = Co (Wig)/"*"*" V" 4 -4
(cent J 18
Cl 18 ^=-2.9 -4
NO 3 18 ^=-4.5 -4 CO
Br~ /8 =-8 -4
18
C10 4~ 18 fe^-9.0 -4
( 8)
10 3 A= 2; 10 4B= 1 0.0009-0.07 25 2.30J -3
buffers ^ = 0. 1 feA + 2*^ AXt
X 4 = (CH 3 ) 3CCOO Sfe /8=1.02 0
~
CHgCOO" 25 fe =7.0 -1
CH 2OHCOO~ 25 ^=1.96 -1
CH 2C1COO~ 25 fe 4 =5.7 -2
H 2PO 4 25 fe J =5. 11 -2 Oi
X = CU+ ( 24)
10 3A=4; B<A 0.00 5-0. Oil 3_ 3
CH C00~ 0.00 6-0. Olfi 18 fe =1.33 -3
3
CH COOH 0.01-0.1 J 18 fe' = 1. 22 -1
3
18 fc"=4.09 -1
18 "'=!. 14 +2
X = Ni^l
CH 3coo r 18 fe'=8.25J 0
CH 3COOH J 18 fe" /=6.(DJ-M
.94 (")
Ac90 10 % - 4. 2 HBr 0,245 feA 25 2.77 -4
(16M/D to 6.8 0.245 25 2.93 -4
A-CH 0
0.303 25 3.85 -4
I l' ! n 3-5 0.352 25 5.36 -4
<v \ CHCH 8C6H4 (o-COOH) + Br 8
CO
\/Vo cr
(X)
( 2-O-c ar boxy ben zl i ndan-1-one) 9
L^UV/UVk>
P^POOP on H ^ -4" 10 3A = 5-25J -<U/dt=*A 25 3.0 -5 * (*)(")
.95 H In ffDi
PRT* _ H 2
10 3B = 1-3 Oi
-4 * <>(",
.96 BrHC(COOC 8H 5) 2 + Br g ^-^ ffl8B=2 HC10 4 0.0011 teA 25 2.6
V
CHgClCOO" 0.05\ 25 6.2 -4
CHC1COOH 0.05J
2
CHgCOO"
0.0021 25 6.0 -4
CHgCOOH 0.002J
teAX 25 6.9 -3
X=CH 2C1COO"
CHgCOO
25 1.7 -1
Nitriles
TT rt
0 >2 -1 ()
.99 CHBr(CN) + Br H 80 ^A *
-5 (")
.100 C^OC^CN + Br a H 8 B A -dA/dt = kk 0 7.1 *
Oi
10 2.3 -4 17 2 9
,101 0 8 -2 * (")
C 8H BOC.*OCHBrCN + Br 8 H aO
*Nitro- compounds
* (")
.102 CH 8 CH 8NO a + Br g H 80 A = 0.3-0.4; kA 26 4.1 -8
B = 0.02 35 1.23 -7 23 1 9
-9 (")
.103 CH,CH8N0 8 + I, H . A= 0.5-0.4; kA 15 9. 1 *
10 3B = 2-7 26 4.0 -8
(X) 35 1.27 ,7 22.9 1.2 9
( 28)
" A = 0.1-0.2; C 5H 6N = A feAX 17 6.07 -5 *
10 aB = 2-4 25 1.49 -4
35 3.57 -4 16.6 AS* =-25
j j 3 3 3s
S96T
Homogeneous Reaction Kinetics
312.47i 18
COMMENTS
General. See comments 1951 edition. For ke tones and keto- respect to A as k/ A almost constant. At lower concentrations
aclds rate determining step considered to be enollzatlon reaction more nearly second order with respect to A and k/ A2
and or ionlzatlon of C-H bond. The rates and rate constants almost constant. Authors suggest mechanism involving an In
listed are for rate of disappearance of halogen, unless termediate A-B complex consistent with data. Decomposition
otherwise specified. Since replacement of first hydrogen of complex found to be first order and rate law determined.
by halogen is generally slower than replacement of second (.45) Rate law not confirmed, except that it Is an over-all
or third hydrogen on the same carbon the measured rate of third order, as A = B in all cases. Addition of t-butyl-
disappearance of halogen may be two or even three times that CO
peroxide reduces rate about 25 (.46) Rate controlling
of the rate controlling enollzatlon or lonizatlon. Since step considered to Involve reaction of OCl" with enol or
organic compound usually, is in excess of halogen measured enolate ion rather than rate of formation of enol and enol ate
rates are pseudo zero order, and first order rate constants ion. Hydroxyl ion effect attributed to shift of enolate ion
are obtained by dividing pseudo zero order rate of dis equilibrium as doubling OH" increases rate by only 50$.
appearance of halogen by concentration of compound being (.47) First order constants calculated from pseudo zero
CO
halogenated. order rates corrected from 1951 edition in which rates were Oi
Oi
Literature. (*) ( 2) ( 8) ( 4) ( 5) ( 6) ( 7 ) ( 8 ) ( 9 ) converted from in equivalents of halogen per liter rather than M/l as
original minutes. ( n) ( 14) ( 15) ( le ) ( 17 ) converted from stated. (.48) Rate of enolization, considered to be
original minutes and from ml. of N/50 thiosul fate per 30 ml. rate controlling step, wouldbeone third calculated rate as
18 20 21 22 23 24 25
from original second and third hydrogen replaced more rapidly. (.49)
minutes. ( 27 ) converted from original hours. Data may be represented by sum of second and third order
Reactions. (.44) Pseudo first order with respect to B over terms with respective catalytic constants or in terms of
about 65$ of reaction as A in sufficient excess. At the higher concerted termolecular mechanism of C 28 ). (.50) Rate
concentrations of A reaction approximately first order with of enollzatlon, considered to be rate controlling step,
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Homogeneous Reaction Kinetics
318.471
COMMENTS (continued}
to acid hydrolysis of ester occurring simultaneously. one determination. (.102) (.103) Assumed to proceed
(.98) Rate determining step probably ionlzation with ioni- through rate determining ionization. One drop of strong acid
zatlon of inonohalogenated nitrllemore rapid than first step. added to minimize competition by OH~. In presence of RN
Dependence of rate upon concentration of Br g and HBr may be reaction assumed to proceed through slow bimolecular Ioniza
related to a lower reactivity for Br ". (.99) Reaction tion, RN + CH CHJC) > RNH* ++ CH CHN0 2~, as rate con-
CH g CHNO
measured In presence of CH 2 (CN) g, see (.98) and only one trolling step followed by rapid reaction between l a and the CO
determination. (.100) (.101) Consecutive reactions with carbanlon. (.104) (.105) (.106) (.107) Rate determining
(.101) determined in presence of some C^ eOCOCH 2CN and only step assumed to be ionization.
ca
LITERATURE
(*) L.J. Andrews, R.M. Keefer, ACS 1953, 75, 3557. ( 2) P. D. Bartlett, ACS 1934, 56, 967. ( 3) R.P. Bell,
D.H Everett, H. C. Longuet-Higgins, PRSA 1946, 186, 443. (*) R.P. Bell, H.L. Goldsmith, PRSA 1952, 210, 328,
( 5) R.P. Bell, P. Jones, CSL 1953, 88. ( 6) R.P. Bell, O.M. Lidwell, PRSA 1940, 176, 88. (7 ) R.P. Bell, H.C.
Longuet-Higgins, CSL 1946, 636. (8) R.P. Bell, R. D. Smith, L.A. Woodward, PRSA 1948, 192, 479. (8) R.P. Bell,
M. a?lro, CSL 1953, 429. ( 10 ) R.P. Bell, A. D. S. Tantram, CSL 1948, 370.
t 11) T. 0. Bonner, D.P. Evans, H.B. Watson, CSL 1939, 1353. ( 12) M.N. Das, S. R* Palit, J. Ind. Chen. Soc. 1949,
26, 322. ( 18) M.N. Das, S. R. Pallt, J. Ind. Chem. Soc. 1950, 27, 179, ( 14) D.P. Evans, CSL 1936, 785.
( 15) D.P. Evans, J.J. Gordon, CSL 1938, 1434. ( 16) D.P. Evans, V. Q. Morgan, H.B. Watson, CSL 1935, 1167. ( 17 ) D.P.
Evans, J.R, Young, CSL 1954, 1314. ( 18) C.K. Ingold, C.L. Wilson, CSL 1934, 773. ( 19) R. Q. Pearson, R.L. Dillon,
ACS 1980, 72, 3574. (*) R. 0. Pearson, R.L. Dillon, ACS 1953, 75, 2439.
LITERATURE (continued)
CO
( 21) R.G. Pearson, J.M. Mills, ACS 1950, 72, 1692. ( 22) R. G. Pearson, F. V. Williams, ACS 1953, 75, 3073.
( 23) K.J. Pederson, JPC 1933, 37, 751. ( 24) K.J. Pederson, Ada. Chem. Scand. 1948, 2, 252. ( 26) K.J. Pederson,
(b
Ada. Chem. Scand. 1948, 2, 385. ( 26) J. C. Reld, M. Calvin, ACS 1950, 72, 2948. ( 27 ) G. A. Russel, H. C. Brown,
-,-^n <~ r
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8 , U8lUU,oo * *
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O
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f = t i
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Homogeneous Reaction Kinetics
312.472
o> k = A ~
c o o
4-1
CO * L. kQ x I0n A x l)n CO
c cd a D H 3
Amount of 0 0) E
c z i 1 Amount of C
No. React ion Of f 0)
1 '-o -o
s ro f c E L.
react ant addend 0 E 0)
<x5 36 C - L O
^ E fe A n O
0 H- O O
n
h- -J
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0
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Homogeneous Reaction Kinetics
312.472
O)
c k A
w
<a 1
Temperature 4 x I
Comments
C & Amount of Addend (Catalyst) Amount of
h x L
i
terature
E
No. 1 M Reaction S
T3 C
reactan t addend <D 0
C k
i I n n
C O
CO o ed
Q
.288.1 J,3-(CH i),C6H4 -HICl Ac 99* A = 0. 1-0.2; ZnCl 2 0.40 *AB[^C1 2] 25 1.18 -3 (26.)
10 3 B = 3-7 0.80 25 1.85 -3
CO
1.40 25 3.33 -3
0.40 45 8.31 -3
0.80 45 1.30 -2 18 5 10
Ac* (') (X)
.289 1.4-(CH 3) 8C6H 4 + Br 2 A = 0.096 ZnCl 2 0.125 kAB 25 1.43 -2 *
-2 CH-
0.25 25 4.7
0.50 25 1.03 -1
CO
.289. 1 l,4-(CH g) 2 CaH4 + IC1 CF,COOH 10 2A= 5.2; 10 8B=4 kAB 25 -2 ( 1.}
O
7.8
2.6 4-8 25 8.8 -2
1.3 4 25 1.05 -1
.291 l,4-[(CH a) ac] 8C6H 4 + Br 2 AC* A= 0.08 ZnCl 2 0.50 feAB 25 1.97 -2 * C)
time % re acted
.292 1, 2,4-(CV 8C9H 8 + Br 2 Ac* A=0.10,*B=0. 10 (10)
25 144 10 *
0.10 0.10 25 390 20
0.02 0.01 25 51.2 (14)
10
Ac 85* 0,005 0.01 25 18.4 10
0.01-0.2 25 k 4.8 -4 15
0.01 25 fe 23. 68 0
0.05 " 25 fc 23.43 0
0.2 25 k2 2.78 0 6.8
25 k^.b -4
0.7 "
0.7 " 25 * 2 1.32 0
25 fe^.38 -2 17
0.05 " NaC10 4 0.10
n M n 25 k 1. 10 +1 6.5
n n 0.15 25 fe t 1.93 -2
n n H 25 fc 22.08 4-1
0.25 25 fe^.02 -2
0.0&-0.1 "
n N N 25 fe 23.25
\ P H RT* o
-4- ^ * (*)
^'A'***
.294 . 18 ^t **> I./Vyfl _/
1 fi PL, f\ r^V AcD90* 10 3A= 3.8; 10 2B= 1.2 NaOAc 0.099 ^AB+fcX 25 fe t 2.97 -1
n n 25 fe 22.05 H2
(continued) -1
C H Cl A=0.19; 10 3B=3.8 /? AB 25 2.46
19 25 2.98 -1
38 25 3. 10 -1 03
( S8 )
ACC90* A=0.2; 10 3B=4 25 1.33 0
AcB90* n n 25 1.47 0
-2 ( 27 )
cci 4 A=0.7; 10 2B= 1-2 H20 -50$ sat feAEM* 17 1.27 Ob
n n 0 %sat 25 3.0 -4
n n 40 % sat 25 2.6 -3
N n 80% sat 25 1.23 -2
HBr 0.01-0.06 25 6.8 -3
~0.1 0.5
0.26 25 4.5 -3
Oi
0.31 25 3.7 -3 Oi
IT ft /X50 ^sat 34 4.7 -3 -11
H 2
cci 4 A=0.2;10 3B = 11 IBr 0.001 feABtlBr] 2 14 9.2 +2
( 10)(88)
4-2 _. ,1<K
0.1 9 0.0008 25 9.8 I >
n 25 9.2 4-2
0.2 2-19
N 25 7.3 +2
0.7 9
n 25 5.5 4-2
1.4 9
H 25 3.6 4-2
2.8 9
25 9.7 4-2
0.2 9 0.0004
25 7.8 4-2
0.2 9 0.002
36 8.2 4-2 -0
0.2 11 0.001
0.06-0.1 t [J 25 6.1 -2 (,
.294. 1 1,3,!HCH 3) 3C6H 3 +IC1 A=0.1; 10 3B=7 -a.
Ac 99* 25 7.2 -2
0.05-0.1 4 0.20
25 6.7 -2
0.2 3-8 o.ao
0.40 25 9.2 -2
0.2 4
25 1.46 -1 4 10
0. 1 4 0.80
h =
Supp
1
ementngi
-M Demasfineds Temperature fe x A x 10 Comments
1951
No. Sol
vent Amount of "0 W Amount of actiawion L
i
terature
No. C >-.
React i on
reactant o <tf addend
TJ -*-
<c a5 k n n
o
.294. 1 1,3, &-(CH 3) 3 C6H g 4- IC1 AC 99* A=0. 1-0.2; 10 3B= 7 0.06-0.1 -1 (86.)
aid, ^cg 45 3.22 16
(continued)
( la)
cci 4 L0 2A=71.2;10 3B = 3-10 fcAB 3 25 7.S7 0
35.6 5 25 2. 16 4-1
14.2 5 25 5.76 4-1
CO
7.12 3 25 9.34 4-1 R
4-2 ^J
1.02 10 25 1.88 ^
-4 r*^
0.99 1 46 1.21 . 4-2
CO
3
.295 Ac* 10 2A = 2-4 -2 () CO
1< 3' &-( C 2H 5) 3C 6H 3 + Br 2 ZnCl 2 0.0125 fcAB 25 6.3 * J3
0.0312 25 1.94 -1
155 H)
k == A
c
-H Demasfineds Teremperatu * x J0n A* x 10n
T3 W
actla*ion Comments erature
tLi
V X Amount of Amount of
C >,
No. 6 rH R e ac t i o n > '-5 g
-a J
$ reactant addend
CO -^
Q. **^s 0 n n
CO
-1 (")
.297. 1 ^3^(CH 3) 4C6H a + ICl 2 Ac 99* A = 0.08; 10 3B=4-7 7nCl 2 0.08 .ABtzaCg 25 1.29 1.0 11
0.05 45 3,54 -1 16
( continued)
.298 AC* 10 2A= 4-8 ZnCl 2 0.0312 feAB 25 6.7 -2 * ('H 19)
* '^3462 2
0.0625 25 2.42 -1
Ac* *
( 29)
.300 (CH 8) 8 CflH + I Cl-^ A- B=0.01-0.02 24
-1 ( U)
CC1 10 3 A= 244; 10 3B= 5 fcAB 3 25 4.92
97 2-7 25 1.65 0
49 3 25 3 18 0
09 k = A =
M- CO 9 L.
c
H ""Z* fj d <0 k x ion L.
-o w 0 -c, 3 3
c<D ^3 Amount of E - -H >4 x io n -H
C >i c
No. React i on > '-5 ^ S -o c cd 4) (d
o <d c -o 0 0
S E
o | re act ant <D o
<t cd
o ? c e" H
k 4 0
0 e
<c H- 0 n n O
<D d _J
Q
.304 C.H.OH
O O
+ I H 0 A=0.01;B=0.001 HO Ac ! pH ftAB; ft = kn 4- ft f [HO Ac] *( 30)(34)
NaOAcJ 4.66 25 feQ 2.90 -4
" " 25 ft 3.66 -3
R 4,96 25 k 5.56 -4
0
n n 25 ft 1.46 -2
-3 CO
n 5.26 25 ft 1. 10 K
if n 25 ft. 5.96 -2
H 2P /1 feABjfe = fen - fejH^PO/]
-5 CO
HP0 4~ j 6.00 25 ft 6.7
tt n 25 ft 3.3 -4 <*>
n 6.40 25 feo 1,5 -4 c**.
it n 25 ft 1 2.2 -3
ti 6.70 25 ft 3.0 -4 Ki
CO
n n 25 ft>- -3
n 7.12 25 ft 9.5 -4
0
n n 25 -2
-j
10 3A= 8; 10 3 B = 2 0.024! -2 * (>
feAB 25 1.30
Na*HPOj 0.008J
0.045! 25 1.57 -2
8 ' 1 0.0 15j
0
11 o.ao! 25 1.85 -2
- } o.oaoj
8
FH '} 0.032! 25 9. 17 -3
CO 0.008J
O ^
a 0.0641 25 1.26 -2
0
0.0 16J
1 o.oso! 25 1.42 -2
' 0.03DJ
National Bureau of Standards - National Research Council December, 1956
Homogeneous Reaction Kinetics
312.472
12
09 o k = A
-M W S
i. 0
** 'eT 3 k x io n m
"O W 0) Of H
C *: o -o r x ion 3
9 3 Amount of C >, E 03 C
No. R e ac t i o n > '^ -0 Q) ^ * TJ C E U
reactan t 3 -O 0 E
~o * C Q.
"*"*
3 O
fe n A n 3
^"^ 1 * H^ 0
o <a ^~~i '
Q
" 1
o.o iel 25 1.48 -2
J 0.16 J
10 3A= 8; J0 8B= 4 -2 ( ?)
Ac ID* NaOAc 1.0 25 1.50
M30*
8 2 KH 2P0 4 1 0.025] 25 1.20 -2
Na2HPOJ 0.0 12j
Di 3D* 8 2 0.02 1 1.30 -3
" 1 25
J 0.01 J
Ag"^" +
.305 C-H-OCH- + HOC1 H 2 10 3 A= 3- ID; 1D 3B= 2 0.005-0. 1 kB
DO 9
-4 / 15\
80
H 24 0.011 25 3. 1 *
IT
6.6 0.5 HC10 4 0.009 25 1. 1 -4
( )
TT f\ -4 (")
.305 C H OCH + HOC1 (continued) H 3 10 3 A=7.7; 10 3 B=6.0 HC10 4 0.012 fcB 25 7.02 *
65 3
" 12.0 n 0.012 25 1.06 -3
n -4 ( 16 )
3 8 0.1 25 6.3
n -3 ( 1? )
6.6 0.2-1 0.6 25 1.3
10 1 HC1 0.0002 feB[HCl] 2 25 3.57 +4 C34)
D1W50* 10 3 A=6.6; 10 4B=7 AgC10 4 -nl 0.16 } feB -5 *
(")
0 5.00
HC10 4 J 0.0 12)
n n n n 25 1.55 -4
8.0 5 n o.oesl 25 2.35 -4
0.05 J
15 5 it 25 2.65 -4
28 5 n 25 3.25 -4
6.6 7 n 0.16 1 35 2.75 -4
0.0 12J
.306 4J?
. 1Q
AC* 10 2A= 2.5; 10 2B= 1 NaOAc 0.068] fc AB 25 1.6 -2 *
(83)
653 2 time % reacted
LlBr 0.035J
25 84 10
( w)
A = B = 0.00625
222 3D
time % reacted
Ac* ( lb )
.308. 1 C6O H OOC H O + Br A A=0.01; 10 3B= 1 k AB 20 86.5 30
^ 0.0^-0.003 -2
to " ( 0.03 25 1.68 CO
d J
0.03
W " 25 2.43 -2
0.045
d g
11 g *-. + , [HPO;=] +*8 V<;]
25 k o 2.05 -3
o
C! 25 fe^.88 0
o
rH 25 k 5.0 -3
35 fe o 7.58 -3 24 (")
OD
d 35 fe 1 1.48 +1 30
H 2 3D 3A= 0-8; 10 8B= 1-4 II ^j 0. 1 feAB 25 3.46 -2 * ( 8)
S 0.15 25 1.52 -2
s | 0.2 25 8.58 -3
13
11 * W 0.3 25 3.82 -3
o
rH -3
2 i 0.4 25 2.15
CJ
o 0.5 25 1.38 -3
M30*
5
1Q 3 A=8; 10 3B= 1 Na2HP0 4l 0.02 -2 ( 8)
feAB 25 1.81 *
KH 2P0 4 J 0.005
00
w
\ 0.03 2.50 -2
d 25
LO " J 0.075
o S
to 0.05
25 3.93 -2
II 0)
0.0125
w w * = Ao + fe 1 [HPO 4=]
0
25 feo 3,90 -3
1 25 -1
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Homogeneous Reaction Kinetics
312.472 17
W 0
k = ^ =
H s- 0) *
-CT W (0 cb 3
k x ion A x ion fa L.
0 TJ E ^ M 3
! I Amount of C >^ *J C
03 C
No. React i on -o ^ T- -o c L. $ 0) <aL.
3 " Q 0 E
o J? re act an t < OJ C 0. E
w ^ o E fe X
J " M- O n n cS ^
Disubstltuted Benzene
Alkyl, Hydroxyl (Alkoxyl)
.318 ~ CH 3C6H 4~ * HOC1 H 20 10 3A= 2-10; 10 3B^1 NaOH 0-0.01 fc AB 25 2.08 4-4 * ( 34)
.319 ra-CH gC 6H 40~ 4- HOC1 H 2 10 3 A= 2-10; 10 3B^1 NaOH 0-0.5 fe AB 25 7.3 4-4 * (**)
H"*" 4-4
3 x 10" 8 25 5.8
.320 -CH 3C 6H 40- H, HOC1 H 2 10 3 A= 2-10; 10 3B^ 1 NaOH 0-0.01 fe AB 25 1.50 4-4 * ( 84)
3.62 4-4
2 1 HC1 0.0002 feB[HCl] 2 25
KI 0.12 J
10 3 A=8; 10 3B=2 k AB * (7)
Di 3D* KH 2P0 4 0.02!
Na2HP0 4 o.oi r 25 1.45 -3
KI 0.1 J
k = X =
Addend (Catalyst) Amount
of Demasfineds 1
Temperature k x i 1
\
Comments L
i
tI
ererat i
No. c | Amount of act1awion
Reaction addend
re act ant *
^-^ A
n n
.327 4-CH 3CH 2CH 2C6H 4OH + I g > (2) Ac 10* 10 3A=8; 10 3B= 4 NaOAc *AB -2 *
(7)
25 2.38
KI 0.03J
h = A
K Defmassined k x 10n
vent
Sol (Medium) Amount of o ro of
Amount 1ton
aw
act erature
Temp x I0n Comments terature
i
L
C >i addend
No. React! on 0 S
-0 a)
reactant T3 +J
O
k n A n
to k = A =
n 9 CD
^ m of rt ^ x 10n ,4 x ion 0}
Amount of c >^> 0 -o E -M 3
<D _ -H ^ C
No. Reactl on
1> 7'-5 -o c 8 ttf
c -o fl> 0 k.
5 I reactant "O -H c .-. E
J ' 0)
v-"> -H . 1
0 *- 0 k v!
n n 0
0 Of
O -J
MMMMH
M30* 10 3 A=8; 10 3 B= 2
.332 4-CA.ayjw. *..-< KH 2P0 4 0.025] feAB * 0
25 2.72 -2
Na2HP0 4 0.012f CO
KI 0.12 J c*
time % reacted
AC* (")
.333 ~^3 } 2 C6 E4 + Br 2 A = B = 0.0031 25 91.3 10 *
25 221 ao
.334 -(CH3o> 2c8H4 + Hoa H 20 10 3 A= 4; 10 3 B= 2 H A?4 0.011 1 feB *
(-.
25 3.1 -4
0.005-0. 1J
time % reacted
.335 -(CH 30) 2C6H4 + Br 2 Ac* A= B = 0.0125 ( 19 )
25 336 10 *
n 25 763 33
0.00625 25 1,220 10
25 a 733 33
Disubstituted Benzene
Alkoxyl, Carboxyl
-]
.336 p-CR OC H COONa + HOBr H 20 10 3 A=7-14; 10 3B=4-5 Na2HPOl 0.01-0.03 feAB * t 30)
3 64
KH PO J 0.002 22 1.1 -1
2 4 J CO
N 0.004 22 1.6 -1 R
^
n 0.006 22 2.2 -1 13
Na2HP0 4 0.011 1 k AB
22 1.32 0
KH 2P0 4 0.002 r
KBr 0.0017-)
Disubstituted Benzene
Alkyl, Amino
to k = A =
** **c m * L. 09
c T3 CD 0 -o cd cd 3
k x !0 n X x lDn 3
O
*3 Amount of C >i E -M C -*-
No. React! on > '-5 C O td
-O 0) c -o TO C IF
~~ 0 "O *-" 0
E t.
reactant o 1 O E V
co *"* c a. ."t!
0 . "*- k X 5
-1 H- O E n n
C OS -
Q
<1 c c c CO CO
s.u.^00 * -X- * * * * *
S9
II
-
c e -1- + -1- + i i i i t i i i i i
91 , .
48 c ^ o S S 5 00 CV2
8 ^233?$
<? 7* ^ m
- -1 IS !S 88 8 8 8 898888888
d
.., uo,v
3 9 5
SSB tu peu \&Q * - *! 9
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tH
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TH 0
o
o ^
o o o
S 2 ^ S C 0 ^
O
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o ...
o o o
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s *
N 0
0 O
i 1
(}S/|B}BQ) 03 O
r-H
8* 8* rn d EC 0 05
w w co H 0) T3 Z X 01
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-u >> 3 *>>
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to (0
f>
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to EC w
to
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0 c J> o 9 -H pq Pq
t 5 Q
H
Q
C5
Q
CO
O
9 9 ^=H TH
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9 w n II II tl tl
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o o o i i O O
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0 0*
S 02 ca oa 0 0
TH
o o o o o
CQ tO 25 Z 25 0 0
t 1
(D
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0
z
? ? ? I i 00
S5
0>
55
Homogeneous Reaction Kinetics
312.472
w k = k =
M- CO f. <D
tt n) 1_ k x jon m
Amount of -o w o -o E a ^ x ion 3
No. 1 | C >-i -*->
React ion ? S T3 C td I at
-o 9 0 V. E u
0 | re act ant ~O -H I i C 9 E a>
t or a. fe A 0 -
o -i M- O E n n O
0) D _J
a
-1 ( 14 )
.354 ^N0 A0CJTOCH(CHJ _ 4 HOBr Ac 75* 10 3A= 2-10; 10 3B= 2-10 fe AB 20 6.42
O 4 d <
-1 ( 14)
.355 -NO C H 0(CH ) CH -* HOBr Ac 75* 10 3 A= 3-10; 10 3B= 2-10 feAB 30 3.60
CO *- j| =
m 9 4)
1 "i -H k x ion A x ion 09
3 V 3
Amount of o co E -H
* '-o 4- g oi O
No. R e ac t i o n <x> _ TJ C ff
0 * T3 (d 3 -o o O
reactant TJ -4-1 C - E
o Q.
< ^ O
fe n ^ 0
0 0 05 i n
Q
Disubstituted Benzene
Aryl alkoxyl, Nitro
.357 P- N0 2C 6H 4OCH 2C6H 5 + HOBr Ac 75* 10 2A- 1-2; 10 3B=5-8 kAB -1 ")<")(") CO
20 1.14
*
Disubstituted Benzene
Amino (Amide) , Nitro
Ac*
,358 -"WW.*-. 10 3 A= 1; 10 4B = 1 NaOAc 0.068) feAB *
<">
25 1.42
LIBr 0.035J
0
.359 Ac* -5
m-NO_C H 4NHCOCH-o + Cl Q A= O.ljB = 0.07 25 6.7 *
()
A O
*
Disubstituted Benzene
Alkoxyl, Halogen
H-
m <D k = A =
H CO *
+* "^ (0 0) 3
-o eo 0 -o 00 L.
C = e *-* k x I0n A x I0n
fl> 3 Amount of c >-, -M C 3
05 c +J
No. React i on > '-5 -o "5 ^ c S 0> 0}
C o L.
reac tan t c Q. O
-H
1 o
1 l
M- 0
6
47
1
fe n ^ n 0
0> CO
Q _J
Disubstituted benzene
Aryl (diphenyl) , alkoxyl
* ( 8B)
.382 *>-CaH 6C6H 4OCH 3 + Cl, Ac 99* 10 3 A= 5; 10 3B= 2.5 HC1 0.01 feAB 20 1.24 0
10 5 0.02 SO 1.27 0
-1 * ( 85)
.383 Ac 99* 10 2A = 1; 10 3B=5 HC1 0.02 ^AB ao 3.72
-1 * ( Z5)
.384 4'-NO,C H 4C H 4-4-OCH 3 + d. Ac 99* 10 3 A= 5; 10 3B= 2.5 HC1 0.01 feAB 20 1.32
10 5 0.02 ao 1.38 -1
0) fe = A =
-M '"""*
09 9
M- oi a) Lo ^ in^ >J x mn m L.
Amount of 0 -D E 3
No. React ion i O (0
"j a
0 re act ant C
CO ^ x 1
fe A 4-*
0 i S H- U n n
O J
Q ^~
.400 4-BrC H CftH -4'-OCH_ + Cl AC 99* 1D 2A= 1; 10*B= 5 HC1 0.02 fe AB 5.70 -1 *
( 8S)
O 4 O 4 w <
ao
.401 4-F-C H ACAH -4'-OC 0H + Cl Ac 99* 10 2A= 1; 10 3B= 5 HC1 0.02 feAB ao 1.53 0 *
( 8B) CO
O 4 D 4 * O
Ac* 10 2 A= 1; 10 3B= 1 ( lb )
.404.1 1.^5^3 A *BT, ft AB ao 2.5 0
(coumaran)
(chroman)
k A o
o L.
nedmass
i
Def 1aw
act
ion l_ k x 10n A * 10n tsn
Comme 3
Amount of Addend (Catalyst) of
Amount ad end D M
-- d
No. Reaction 5 * L.
L.
i* 1'-5 O
reactant -H
d. fe ,4
a i n n _J
I
CO
Three substituents on Benzene
Dialkyl, Halogen
-2 (1.)
.405.2 1,4-(CH 3) 2~2-IC6H 3 -f id CFgCOOH 10 2A=4.7; 10 3B=4 feAB 25 3.2
2.3 4 25 3.7 -2
CO
(0 fe =
CO * 0
X = o
cd (0 k.
c f. -o w E 3 fe x ion A* x I0n 3
0 3
Amount of o -o C -M
No. R e ac 1 1 o n c >, .j C TJ C cd 05
* -o
TJ Vt c * c o E
reactant "O -- 3 ^ C E
^ 1 < ctf Q. 0
O H- O e ^ n 4 n o
J C _J
0 i
.438 l-C 2H B-4-(o-H0 2C6H4CH 80)- fr B^C6H 3+ Cl 2 Ac 99* A = 3B ^0.01 HC1 feAB ao 1.50 -2 * ( a4)
.439 l-C 2H 5-^(P-N0!!CaH 4CH 20)- fr B^C6H 3 + Cl 2 Ac 99* A= 3B^0.01 HC1 feAB ao 1.63 -2 * ( 24)
CO
.440 l-CH 3 CH 2CH 2-4- (o-N0 2C6H4CH 20)-8,Br-C6H 3 + d. Ac 99* A = 3B ^ 0.01 HC1 k AB ao 1.08 -2 * ( 84)
.441 1-CH-CH 0 CH -4- (-NO-C-H.CH_0)-&-Br-(LH + Cl Ac 99* A = 3B ^0.01 HC1 *AB ao 1.23 -2 * ( 84)
322 r 2642 63 2
.442 1-(CH ) 0-4-(o-N0 0C H CH 00)-5-Bi-C -H +C1 0 Ac 99* A= 3B ^0.01 HC1 fe AB ao 5.60 -3 * ( 84)
33 & o 4- o 3 H
.443 1"" f CH ) C~~ 4~~ ( b~ NO C H CH 0 ) ~ &~ Br*"~ P H ~f~ PI Ac 99* A = 3B^0.01 HC1 /? AB ao 6.55 -3 * ( 84>
.444 l-(CH) O4-(2',6'-Cl C H CH 0)-5-Br-C flH + Cl 2 Ac99* A = 3B~0.01 HC1 feAB ao 1.16 -2 * ( Z4)
33 2642 63
.445 1-(CH ) CH(CH ) -4-C H CH 0-6-Br^C H + Cl \ ^ 99* A = 3B^0.01 HC1 feAB 3D 2.63 -2 * ( 84)
.446 l-(CH 3) 2CH(CH 2) 8-4-(o-N0 2C6H4CH 20)-5-Br-C6H 3 + Cl 2 Ac99* A=3B~0.01 HC1 /e AB ao 4.28 -3 * ( 84)
.447 l-(CH 3) sCH(CH 2) a-^(^N0 2C6H4CH 20)-^B^C6H 3+ Cl 2 Ac 99* A=3B-0. 01 HC1 feAB 3D 5.55 -3 * ( 84)
.448 l-OH-2,4-Br -C H + Br o AcW72* 1D 8A= 5; 10 SB= 4 HC10 4 o.iol feAB ao 5.3 -1 * ( 88)
263 2
LlBr 0.10J
Acweo* 7 HC10 4 0.10 1 ao 2.4 -1
LlBr 0.137J
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(Modi urn)
P> '*
H
Addend
(Catalyst)
Amount of
addend
Defined mass
>->>>>>> E J s i E s act ion 1 av
B8BB8BBB Temperature
8 B 8 B 8 B B
O tD 00 i-J- CO M- CD ^ODO3H-f^rOc>3tO
o& ^ go o c& 03 CTI d^. --3 OQ CJ1 O <I *o *o
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11
3 83
Comments
L i terature
Jf J? J J J J? J J? J J J J? J J J
9561
6 $ 5 5 5 5 5 $ $ O
*
H*- 8 CO 00-1 0> 01 ^ 03
p
r r r r o
03 0? ,03 O3
03 CO
1 O1 Ol Ol C71
Q g Q g SP V V V
^ *!_ **_^ *l *. poop
* 1 1 1 1
1 to tp tp tp t t t t
>< CO O TD o wS , wS
1 M Ml
S 0 1 10
"o 0> 0 0 9 * WS ^ "?
10 to To
10
lO^ S3 S3 W ?o
s > 9
? "o * *0
o W + + U S3
10 -3 -3 10 ffi o> S3 eo
10 10 ^ S3 u 3
to O 4^ +
S3 Oft O
W> 33 0 >-
CA H-- tO
o
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to
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M O
c ?r ff
G ^ Q > Q Q S" S* & o Solvent
CD ^ gcp* e 6^ CD CD CD CD
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9* )-- 9 ffi X S3 S3 Addend
0 0 N
(D P 0 P P
9 OQ <& ** *&? (Catalyst)
o 0 0 O O
9
M 9 0) Amount of
b 0 0 O O M
to to to to to addend
ar 3r 3sr 3r Defined mass
fe bb DO 65 65
ac t i o n 1 aw
Temperature
8 8 88 888 8 8888
o> CO Cb O> 03 ^ *
0 M- $n >> o ^o t^- ct 3r o
& CD rf*- tO
03 M ro o^Njco "^5" o to 01 X
II
o o o o o o o
1 1 1 1 1
3
03 ^ *. ^ rf^ 3
* fca
(D
O OO OOO Oo
cf
p. 0
*,'
* ^ -X- * * * -X- * Comments
10 10 (0 CO
ea w C9 co to to to to Li terature
3 Si
Homogeneous Reaction Kinetics
312.472 38
07 k = ^ =
m 9 c
H 0 "0 ti ti m u
7 3 k * 10 n ,4 x 10n
Amount of -0 (0 c E
c H
No. React i on C > ti o ti
> '^ (D c -o o c ^
3 T3 c o s
0 | re act an t a +> O ti c E
Q. k >l0 O
W ^-x t ti E O
i
o J H- O n n
0
H- !Ij
.482 3,3.-a 2-4,4 I -(C 2H 50) 2- ( C8H 3 ) 2 + Cl2 Ac 99* 10 2A= 1; 10 2B= 5 -2 (-)
HC1 0.02 feAB 20 1.19 *
.483 3,3'-Cl 2-4,4'-(n-C 3H70) 2-(C6H 3) 2 + d, Ac 99* 10 2A= U 10 3B= 5 HC1 0.02 fe AB 20 1.29 -2 (28)
*
.484 3,3'-Cl 2-4,4'-[(CH 3) 2CHO] 2-(C6H 3) 2 + d, Ac 99* 10 2A= 1; 10 3 B= 5 HC1 0.02 20 1.63 -2 ()
k AB *
CO
Five Substituents on Benzene
Alkyl, Alkyl, Alkyl, Alkyl, Halogen
time % reacted
.485 L-n^WU
pti ijr\ A = B = 0.01 30 * (23.)
1, Z, 3, 5- (CH 94
J -4-F-C 6H + Br 0 870 10
k A o
Demasfinesd Temperature k x ion A >c 10 Comments
I
1
vent
Sol (Medium) Amo u n t of Addend (Catalyst) act1awion
No. Reaction S Id
4*
reactant O
n A n 1
1
time % reacted
AC* A= B = 0. 10 25 37,300 10 * ()
.506 l-IC H +Br-^(4)
0.30 25 5,460 10
0.10 HC10 4 0.50 25 3,780 10
0.30 0.50 25 600 10
0.05 0.50 52 3,840 10
CO
0.10 0.50 52 840 10
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Homogeneous Reaction Kinetics
313.472 45
COMMENTS (continued}
CC1 , Seconds converted from original minutes. Induction law folio wed up to 30$ reaction. Pseudo first order constant
period if HBr not introduced initially. Rate law followed expressed by ( 17 ) by the equation k = h o + k 1 [H*] + fe'^H^A
to 90% reaction. Pseudo first order with respect to B, one- with values feQ = 1.25 x 10" 4, fe'= 1.18 x 10" 3 andfe"= 0.473
half order with respect to HBr and zero order with respect in the range studied. Valuesoffeo and k 1 identical for mesi-
to A since Ain sufficient ezcess. Rate constant calculated tylene, phenol, anisole, methyl w-tolyl ether, and methyl
by dividing pseudo 3/2 order constant by concentration of -tolyl ether. See (.293) (.305) (.322) (.323). In presence of
Co
A. Reaction carried outlndarfcto avoid side chain bromlna- HC1 rate constant observed by ( 84) had identical values for R
tion. Strong catalysis by impurities in commercial meslty- phenols and phenolic ethers studied at phenol concentrations
lene. Selected data of ( 10 ) in CC1 4. ( 32) gives rate law greater than value listed. See (.305) (.308) (.320). Rate de
termining step maybeHCl + HOC1 >C1 2 + H20. (.302)
in agreement with ( 10 ) and times for fractional reaction.
(.295) (.296) (.297) Rate law does not Include dependence C H 0~ and HOC1 considered to be reactive species by ( 84)
6 5
on [zhCl. Plot of I/ k vs. [HBr] is linear, which is attri rather than C H OHandOCl" based on study of OH" dependence
buted to the formation of an inactive ZhCl 2 'HBr complex. of rate of chlorlnatlon of salicycllc acid. Units, seconds
Oi
converted from original minutes. (.303) Units, seconds
(.298) (.299) Rate law of (*) does not Include dependence
converted from original minutes. (.304) Selected data
on [znClJ. Plot of I/ fc vs. [HBr] Is linear, which is attri
buted to the formation of an inactive ZnCl 2 'HBr complex. of C 3),! 30). Units, seconds converted from original minutes
times for JD% reaction. (.300) Units, of ( 3), ^M 30 ). Rate law foil owed up to about 50% reaction
( 19 ) gives
seconds converted from original minutes. Ratio of (CH 3) 5C6I by ( 3) and 60% reaction by ( 7). KI also added 0.1 M/l by
C 30), 0.12by( 9) and0.03-0.12 by (7 ). Empirical expression
to (CHJ C Cl estimated from amount of I at infinite time.
356 *
forte developed by ( 3)atpH 5.7-6.6 an d 5.6-6.0 respectively:
The HI formed on chlorlnatlon reacts with IC1 to form un-
(.301) Selected data of ( 17) units, at 25 fe= 10~ 8 x [R+;
reactlve I .
at 35 fc = lO" 8 ^]"
seconds converted from original. Pseudo first order rate
December, 1956
National Bureau of Standards - National Research Council
Homogeneous Reaction Kinetics
312.472
46
COMMENTS C continued}
Phenoxide ion considered to be reacting species and rate dependent upon [KI] and buffer constituents. From pH 5.4 to
constant also calculated in terms of it. (.305) Ag* 7.6 *o is independent of pH. Below pH 5.4 calculated value
introduced by ( 10),( 16) and ( 17 ) to keep Ci" concentration of feQ (extrapolated to zero buffer concentration) falls to
low. ( 15) observes rate to be identical to rate for C6H 4 (OCH 3) 2 9.8 x io~ 4 at pH= 4.57. Units, seconds converted from origi
and C H OH. See (.301) and (.334). Selected data of ( 17 ). nal minutes.
6 5 Rate law followed to about 90$ reaction.
' Units, seconds converted from original minutes. Rate constant (.314) HI formed on chlorinatlon reacts rapidly with id
expressed by ( 17 ) by the equation k = kQ + k' [H*] + ^'Of^A to form I a which isunreactive at stated conditions. Units, Co
with values k = 1.25 x ID" 4 , k' = 1.18 x I0~ 3 andfe" = 0. 109
o seconds converted from original minutes. (.315) Units,
in the range studied. Values of fcQ and k 1 identical for me si - seconds converted from original minutes. (.318) (.319)
tylene, phenol, an 1 sole, methyl w-tolyl ether, and methyl Units, seconds converted from original minutes. Mechanism CO
-tolyl ether. See (. 293) (.301) (.322) (.323). In presence of considered to involves ArO~ and HOC1 see (.302). (.320)
HC1 rate constant observed by ( 34) had identical values for Units, seconds converted from original minutes, in presence
phenols and phenolic ethers studied at phenol or ether con of HC1 and sufficient phenol rate identical for phenols and
centrations greater than value listed. See (.331) (.308) (.320). o>
phenolic ethers studied by ( 34). See (. 301) (.305) (.308).
(.306) (.307) Units, seconds converted from original minutes. (.321) Rate law followed up to about 60% reaction. Units,
(.308) Units, seconds converted from original minutes. Rate seconds converted from original minutes. (.322) Rate
constant Identical to value observed by author for phenols law followed up to 50% reaction. Units, seconds converted
and phenolic ethers studied in presence of HC1 at phenol or from original minutes. Pseudo first order constant expressed
ether concentration greater than value listed. See (.301) by the equation k = k + k 1 [H4"] + fc"[H+]A with values
(.305) (.320). (.309) (.311) (.312) Units, seconds con ko = 1.25 x 10" 4, k' = 1.18 x io~ * and k" = 1.30 in the range
verted from original minutes. (.313) Pseudo second studied. Values of k and k 1 identical for mesitylene, phe-
o
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312.472 50
LITERATURE (continued}
( 21) D.H. Derbyshire, W. A. Waters, CSL 1951, 73. ( 22) A. W. Francis, ACS 1986, 47, 2340. ( 23) E. Grovensteln,
U.V. Henderson, ACS 1956, 78, 569. ( 23a) G. Illumlnatl, G. Marino, ACS 1956, 78, 4975. ( 23b) B. Jones, CSL 1941,
13
267. ( 24) B. Jones, E.N. Richardson, CSL 1955, 2772. ( 25) B. Jones, J.P. Sleight, CSL 1954, 1775. ( 2e) R.M.
Keefer, L.J. Andrews, ACS 1956, 78, 3637. ( 26a) R.M. Keefer, L.J. Andrews, ACS 1956, 78, 5623. ( 27 ) R.M. Reefer, to
j.H. Blake, L.J. Andrews, ,ACS 1954, 76, 3062. ( 28 ) R.M. Keefer, A. Ottenberg, L.J. Andrews, ACS 1956, 78, 255.
( 29 ) L.J. Lambourne, P. W. Robertson, CSL 1947, 1167. C 30 ) B. 8. Painter, F. G. Soper, CSL 1927, 2757.
( 31) P.W. Robertson, CSL 1954, 1267. ( 32) P. W. Robertson, J.E. Allan, K.N. Haldane, M. G. Simmers, CSL 1949, 933.
( 33) P.W. Robertson, P.B.D. de la Mare, B. E. Swedlund, CSL 1953, 782. ( 34) F. G. Soper, G. F. anlth, CSL 1926, 1582.
( 35) C.G. Swain, A. D. Ketley, ACS 1955, 77, 3410. ( 36 ) T. Tsuruta, K. Sasafci, J. Furufcawa, ACS 1945, 76, 994.
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312.473
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Horaogtmoui filiations EXCHANGE Liquid phase
312.474 Replacement of H by halogen on Si
CO k =
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C 6H 6 25 1.77 4-1
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Homogeneous Reaction Kinetics
312.474
Demasfineds Temperature
1 ion Comments
1 terature
Li
1
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acti k* x
Medi um Amount of
No. R e ac t i o n
(Sol vent) re act ant k n
time % B re mainl ng
60
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120 18 46
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2 x ID 5 25 33
3 -2 * (*)
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CHC1 3 6. 1 0
5.8 -4 *
( 2)
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*AB* 1.4 -1 *
( 8)
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1. 1 -4 *
(")
CH 8CaH B A = 0. 14; B = 0.43 *x 23
.22 (^-C1C6H 4) 3 S1H + AgC10 4 > (-ClC6H 4) 3 S1C10 4 + Ag + H 2
COMMENTS
Reactions. Good fourth order rate constants observed over course of reaction and with ratioof A/B varied from 0.5-2.
(.1)
At 55 mixed third and fourth order observed. No effect on rate constant of light, 0 2 orH 20. Light does influence reaction
products. (.2) Initial rate only. Over the course reaction appears to be slightly less than third order. Rate of
hydrogen evolution followed, which was reproducible, although stoichiometry of reaction not always reproducible. Above
0.35M/1 B initial rate appears to be higher than second order with respect to B. (.3) Reaction order assumed
identical to (.1). (.4) Initial rate only. Reaction order assumed identical to (.2) on basis of shape of rate curve.
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Homogfinou Reaction!
312.570 EXCHANGE Liquid phase
Hydrogen by halogen on NH and amine Amounts are in M/I.
Rate constants are In
M/l and sec.
0 k = A =
^_,
: * fe x I0n A* x I0n CO
c E ~
Amount of (0 c
No. React i on PH L. E a>
reactant M E
o 1,c "~ Q- E
CO E
fe n ,4 O
0
n O
*<D (g h-
0
.1 NH 4 HOC1 > NH Cl 4 H 0
3
HO 10 5A=2.3; 10 5B= 1.1 ^.0001 4.58 feAB 6 2.05 ^ *
22 2
" 11.7 6 8.5 41
CO
it 4.58 *4- C 15 4.8 4-1
0 0
rt 11.7 CO -H 17 1.60 +2
E S
H 4.58 25 1.27 42
-M C
.0001 4.71 25 2.17 42
C 0
.0001 6.11 25 3.67 +3
CO
oO
.0001 6.49 -H 4-3
C
25 9.67
J CO
.0011 10.95 -H O 25 1.53 43
CO
.012 12.05 C -H 42
O >i
25 1.23
o
.015 12.23 CD 25 9.7 +1
T> C
c* at
.021 12.30 25 6.2 41
u
~.0001 11.70 0 cd 31 3.07 42
CO -M
n A
11.70 o -*-10 35 4.70 4-2 11.0
w 4,58 37 3.53 42 16.5
4.58 *.A' B/ 6 4.2 46
11.70 6 4.7 46
4.58 15 5.0 4-6
11.70 17 5.3 46
4.58 25 5.8 +6
11.70 31 6.0 4-6
11.70 35 6.5 46
4.58 37 7.2 46 2.5 2.5 10
i
CO <D fe = A =
CO S L. A x I0n 0}
-H fe x lQn -H
<d cd 3
C C
O Amount of E
No. Reaction > cd
M PH T3 C L. i E
reactant O O O E
0 C O-
CO .- ^- E
k n A n &
4- O 0>
<D (d 1
Q
.2 CH NH 4- HOC1 > CH NHC1 + H 0 HO 10 5A=2.3J 10 5B=1.1 [OH"] = 0.12 feAB 6.5 2.53 4-2 *
32 32 2
n tt 12 3.74 4-2
n n 16 4.91 4-2
n 21 8.00 4-2
it ft 25 1.11 4-3 13.8
.0001 4.33 25 2.52 4-2
.3 (CH ) NH 4- HOC1 > (CH ) NC1 4- H 0 H 20 10 5A=2.3;10 8B=1.1 [OH"] =0.12 feAB 6 3.56 4-2 *
32 32 2
n n 11 4.64 4-2
n n 14 5.42 4-2
n n 21 8.64 4-2
tt 25 1.05 4-3 10
.0001 4.09 25 8.7 4-1
COMMENTS
Tabulated values of k are for observed second order rate law in terms of total concentrations of reactants. Specific
second order rate constants in terms of calculated concentrations, A7 ,B', of the specific chemical species are listed as
fc g . The pH dependence is consistent with a reaction mechanism involving NH with HOC1 or NH "*" with OCl".
co
CO
LITERATURE
^_^ XI k =
Amount
of l)
(addend of
Amount Def
i
nedmass ion
act
1aw Temperature
So
vent
I (Medium) Amount of (2)
addend k x K3n
No. React ion -o j_
pH
reactant 5c -
T> *tl CO
< ^ k
11 n a
. 1 CH C'ONHCH + HOC1 > CH^C'ONGICH^ + HO H 0 10 2A= 2; 10 3B=5 CH COOH 0.015 CH 0COONa 0.035 k AB 5.0 25 -3
33 332 7.87
2 0 3
0.040 0.093 5.0 25 1.92 -2
0.080 0. 187 5.0 25 3.58 -2
o.iao 0.280 5.0 25 5,64 -2
0.0038 0.096 6.0 25 3.22 -3
CO
0.0075 0. 192 6.0 25 5.02 -3 01
0.0150 0.385 6.0 25 8.35 -3 a>
(X) k = k + h [x]
CH 3 COOH 0.01-0.1 n 0.04-0.3 5.0 25 kQ 8 -4
0.004-0.01 0. 1-0.4 6.0 25 h o 1.42 -3
5-6 25 k 4.5 -1
CH 2C1000H 25 kX 2.50 0
C H COOH 25 fex 1.03 0
6 o
0~NO C H COOH 25 k 7.33 0
(CH gCOOH) 2 25 fex 1.02 0
HOOC(CH 2) 2COO" 25 ** 3.5 -1
-w M- -3
H 0PO HP0 4= 6 25 1.2
2 4 k*o
0.022 0.0028 6 25 1.85 -3
0.044 0.0057 6 25 2.53 -3
0.089 0.0114 6 25 3.85 -3
..- ' -3
7 25 k0 5.2
0.010 0.015 7 25 5.50 -3
e c 10 tO C\2 02 02 to to to to 0 0 0
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 i 1 1
2
$s
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W
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05
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02
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0.
MB | UOI^OB
s pa
5
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to o
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cd
1 *
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0*
0 H II II
^ ' 8 8n 8
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0 0
(3) pUGppy 33 g
33
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8 5 Q
o o o o
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8 0 0
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O
^
O
00
O
W
O
0
O 88 0 0
0 0
,o >unoV 0 O O 0 0 O 0 0 O O O O O O O O 0 O 0 0
(p JOB Je^ng)
02
tO
-tf
CD 33
O
33
1 ^ 1
33
0
1
(X
o
O 8 8 8 8 O 0
s *N g M
CO
(T ) pueppy x o O 0
O as 33 g
LO LO LO LO LO LO
<+_
II II II II II II
pq PQ PQ CQ PQ
CO CO 0 09 P
S 9 9 9
^ o
OJ w N <tt w w oT
1 2 n II II II n II
0) N 0) 01 01 oi
Q 9 s 9 9 9
(uin |p*w) o o SN oa
33 33 33 33 33 33
01
33
33 0
O 01
8 33
5 g
I
C
iH 33
O CD
O
1
T
0
T xw T
0
03 O
c
0 g 0
33 CO
g
+J
t
0 33
t
o
t
<0 33 -f
CO o n
o 0 +
O CT r-4
w g S rH
a
O
d s";* V T^ CJ
O
i 5 i ?
33*
(D
+
33
O
I
0 0
<o
-<L o *e 0
T I1 0
rH CO
3
10
3- 1
O 0
8 S3 g g
33
0 0
4-
o
S CV2
pH 33 0 33 f^) 33
g
33 um
05
v-4
tO
0 O
1 g 0
g 0 g g
3 o u u
s
O 2 6
g
e 0
g
09
g g g g
o
O ^ ~ CO
t LO CO
z
Homogeneous Reaction Kinetics
312.571
COMMENTS
CO
K
Selected data. Units, seconds converted from original minutes. Rate law followed to about 65% reaction.
LITERATURE
R.P. Mauger, F.O. Soper, CSL 1946, 71.
-o
k =
Amount
of adden
d Def
i
ed
massn I
act
1awon
Amount of Comments
No. co V.
React! on Addend 0
E M-
reactant Q.
k n
C
t
CO
C3
.1 CC1 4 + NH 8 A = 1. 3; B ~ 10 6.5 x JO 4
150 0 *
0.05 150 6.5 x ID 4 ^10
k AL 300 6.5 x 10 4 10 5.3 -4
KI 1.3 300 6.5 x 10 4 84
COMMENTS
For these reactions below critical temperature of NH g see 332.753. Data gives order of ma^iltude only.
Concentrations estimated at reaction temperatures. Reactions proceed through Intermediate which Involves
about 10$ of the reacting carbon for (.2) andless than 5#for(,l). Production of hallde Ion slightly
ahead of guanldlne at all stages.
LITERATURE
0. W. Watt, H. T. Hahn, ACS 1955, 77, 312.
fe = A
Teremperatu U
K V
X
10n A x
Amount of Def \ ned mass - Cosmment
No. React Ion So 1 vent E Ast
reactant action law
fe A
n n
k A
Temreperatu k x 10n A x ion
Amount of Def i ned mass- Comments
No. Reaction Sol vent S A^
reac tan t act ion 1 aw
n A n
\
.8 CH COOCH(CH ) + 2CH NaCOCH CH(CH ) 10 2A=4-9;iOB = l-2 -5
3 32 2 232 CW.o -dA/dt = feAB 0 1.80
30 7.8 -4 20.6 6 11 -7.4
.10 (CH ) CHCOOC H -*- 2CH NaCOCH CH(CH ) 10 2A=4-9J 10B=l-2 -dA/dt = feAB -4
32 25 2 2 X 3 2 W. 30 2.52
O>
.11 10 2A=4-9; 10B=l-2 -dA/dt = feAB -4
32 225 2 2 32
(W 30 1.53
I
.12 GH-OuUU ri_ ~t~ c CH NaCOCH CH(CH ) <W, 10 2A=4-9; 10B=l-2 -dA/dt = feAB 30 2.3 -1
3 DO 2 232 *
.14 C H COOC H + 2CH NaCOCH CH(CH ) <W.o 10 2A=4-9J 10B=l-2 -dA/d = kAB 0 7.2 -2
65 65 2 232 *
30 2.2 -1 6 ^ 4 -43
COMMENTS
General: Reactions studied in presence of excess of alkali metal ketone which was produced by titration with triphenyl
methyl sodium or lithium. Diketone first produced reacts rapidly with second molecule of alkali metal ketone to produce
sodium, or lithium, dlketone so that differential rate equation has the form dx/dt = fe(a-x) (b-2x). "a" and "b" are Ini
tial concentrations of ester and alkali metal ketone and x is ester reacted at time t. Specific concentrations of reac-
tants not stated in each case. When ester concentration was 0.20 and concentration of sodium ketone only 0.24 the above
rate law did not hold. For all data listed concentration of B is greater than twice concentration of A. Authors give
units of Atft as k cals/deg. the units should be cals/deg. Values of E and As are based on measurement at only two temp
eratures so that number after the decimal probably has no significance.
Reaction: (.6) Activation energy and AiST recalculated as values given by authors do not agree with the data. (.7)
(.9) No data given to indicate limiting value of rate constant. (.12) (.14) Value of rate constant in doubt as
reaction too fast to measure accurately.
LITERATURE
K4.
CO
3 " 2 S^UQUJLUOQ
*i o> S
3 v> o
5- -H o
tQ ^ - CQ
05 (0
e
HH"
to to
to to
CV2 CO CV2
o ojuo|
odd
o
-f->
CO d
"5
puoppe
o
CO
CD O
8
CD g&
0)
o
CO
o^
CQ
t +
N
s
CO
IO
OC CO
to
SI 03
O tO
tO
0
X
CD
O
B
x
Homogeneous Reaction Kinetics
333. 363
-H
<D K
s- C L.
k x I0n CO
-o <D 3 -M
-H 3
| ? Amount of H c Def i ned mass 03 C
No. Reaction '5 ^ OT L. <D rt
Addend 5 ' PH <D E
o reactant O action 1 aw O.
O -H
2*
i
<c
k n O
C g
O t
.1 -3 / 2\
W 011 * 2 + H 82 * H 20 10 2A = 1-5 NaC10 4 0.2 4.4 fe xAB + k 2A 2B 25 * 25.0 *
J0 3B = 5-40 0,3 4.5-5.5 fc;= kjK*] 25 ft ^1.2 -7
C.H
O O
ROH + B(OH) ,O
0,3 4.5-5.5 fe' " As [H ] 25 ft ' 1.8 -6
r continue^ 0.5 3-5 ^l" fel^ 25 k ^1.3 -7 ( 3)
0.5 3-5 25 ft 2 1.6 -6
-3 / 2\
10 2A= 3 GlCHgCOOH 1 0.3 3.67 .AB 25 1,45 * CO
0.055
4 ClCH 2COONaJ 0.3 3.67 25 1.61 -3 K
3 0.2 3.75 25 1.58 -3
4
0.22 0.3 3.75 25 1.73 -3
3 CHgOOOH 1 0.3 4.88 25 9.93 -3
0.05
4 CHgCOONaJ 0.3 4.88 25 1.26 -2
1 0.2 5.34 25 1.98 -2
0.05
3 0.3 5.34 25 2.28 -2
( 3)
10 3A= 4-1000; NaC10 4 + k AB *
10 3B^3 ^3 -4 tn
catalyst = X 0.5 k = ko + k x X 25 ko 8
(HOOCCH 2) 2C(OH)COOH 0-0.2 0.5 1.9 25 ft^l.5 0
(CH 2) 5C(OH)COOH 0-0.05 0.5 3.4 25 ft^l.2 0
(CHg) 2C(OH)COOH 0-0.2 0.5 3.3 25 fex 7.5 -1
0-HOC6H 4COOH 0-0.005 0.5 2.8 25 ft x5.9 -1
C6H 5CH(OH)COOH 0-0.05 0.5 2.2 25 /? x 3.6 -1
CH 3CH(OH)COOH 0-0.05 0.5 2.4 35 fex 1.6 -1
HOCHgCOOH 0-0.2 0.5 2.5 35 ftx 3.5 -2
HOCH 2CH 2COOH 0-0.05 0.5 2.8 35 ft x 3 -3
(other chelating age nts see c oinmen ts)
COMMENTS
Literature. (*) Selected data. This appears to be a unique case of acid catalysis where each strong acid gives an indi
vidual catalytic rate law. With perchloric acid as catalyst linear plot obtained on plotting log k co r vs. log of the
product of the activities of the water and the perchloric acid, k cor is observed pseudo second order rate constant
corrected for uncatalyzed reaction observed between pH = 2-3. With sulfurlc acid no simple linear correlation was found
between ^cop< and the activities of the sulfuric acid and the water but log (a* Q x a^*Q ) vs. log & cor gave a linear ^
plot over the range studied. Only in the case of phosphoric acid was a linear relationship observed between log k cor. and T3
^
HO , Hammett 1 s acidity function. ( 2) Selected data. In absence of buffers initial and integrated course rates obey *"*
the rate expression -dB/dt = fcjAB + fe 2A2B. In presence of buffer pseudo second order rate law obeyed but calculated ^
constants dependent upon pH with slight dependence upon buffer concentration and Initial concentration of A and Ionic ^
strength. ( 3) Selected data. Wide variety of chelating agents tested for catalytic activity. No appreciable catalytic K-A.
activity observed for the simple dibasic acids used nor for any of the 1, 2 or 1, 3-dlols studied in acetate buffer at <o
Oi
pH - 4.7. Concentrations of malonic acid and malonate ion each at 0.5 M/l depressed rate about 35%. All a-hydroxy acids Oi
studied showed definite catalytic activity. Detailed studies made using citric acid and a-hydroxy iso-butyric acids as
catalysts relating catalytic activity to pH as well as to concentrations of a variety of ions and complexes.
LITERATURE
{*) H. G. Kulvlla, ACS 1955, 77, 4014.
77, 4830.
CO
(0 9 <D o
cd o5 k - V)
E - -M 3
-M k x ion
| ? Amount of Addend Amount of C
. "0 C t_ 0 0)
No. React i on n 0 0 E
0) <D
react ant (Catalyst) addend c 0. E
* O -H 0
^ CO <v- o E Q 0 ._
<D RJ f n .J
Q
.1 CaH 8B(OH) 8 +Bra + H 80 -^ WAc20 10 2A= l;10 3 B=8 NaBr 0.4 0.4 k AB 25 4.84 -3 * (V t?d
WAC50* 10 3A= 8-40; k AB 25 6.41 -3 * ( 8) S
-3
t?d
10 3B = 2-9 NaC10 4 0. 12 0. 12 25 7.28 tz;
NaN0 3 0.3 0.3 25 7.62 -3 H
Na 2S0 4 0.1 0.3 25 1.27 -2
(X) k= k +fe X 25 k =7.28 -3 CO
0 X o
Na 2H 2P0 4 0.06-0. 12 0. 12 25 fex = 7.2 -2 01
01
CHgCOONa 0.06-0.12 0.12 25 fex = 3,0 -1
C1CH 2 COON a 0.06-0.12 0. 12 25 k = 2.5 -1
0.06-0. 12 0.12 25 k = 1.33 -1
Cl 2CHCOONa
0.06-0. 12 0.12 25 fe = 3. 27 -1
o
C oJTCOONa
NaHS0 4 0.3 0.3 feAB 25 5.06 -3
0.1 0.25 25 4.34 -3
HC10 4
0. 12 0. 12 25 4.16 -3
V) k =
(0 9 0>
f J 1_ 00
e 3 k x ion -M 3
| ^ Amount of Addend Amount of C
No. React ion ._ * LL TJ C CO > as
0 i- e
r eactant (Catalyst) addend e E
1 "5 Q. o O *-
*- 0 E n O
<D 0* 4) _J
Q H-
.7 m-C 2H ROOCC6H 4B(OH) g + Br 2 + HgO WAc20* 10 2A= 1; 10 3B=8 NaBr 0.4 *AB 25 2. 10 -4 ( 3>*
.9 ,-N0 2C 6H 4B(OH) 2 .Br 2 .H 20> WAc20* A = 0.08 NaBr 0.4 kAB 25 1.46 -5 ( 3)*
CO
0.4 feAB 25 1.87 -4 ( l)
.10 m-FC6H 4B(OH) 2 + Br g + H 20 > WAcSO* 10 2A= 14 10 3B= 8 NaBr
10 3A =2-10; 0.70 *
(*)
.12 m-ClC0H4B(OH) g 4- Br 2 + H 20. > C [CHgCOOH] = [fir"] =0.25
10 3 B = 2.5-20 R[CH 3 COONa] [CHgCOOH] =
R = 0.67 pH = 4.7 0 k AB 25 3.55 -1
0.67 4.7 0.15 25 3.60 -1
0.67 4.7 0.30 25 3.39 -1
0.67 4.7 0.45 25 3.20 -1
1.22 4.4 0 25 1.77 -1
1.22 4.4 0. 15 25 1.60 -1
1.22 4.4 0.30 25 1.59 -1
1.22 4.4 0.45 25 1.50 -1
2.33 4.1 0 25 9.55 -2
2.33 4. 1 0.12 25 8.76 -2
2.33 4. 1 0.30 25 7.67 -2
0.45 25 6.66 -2
2.33 4. 1
0 25 3.70 -2
5.7 3.7
3.7 0.15 25 2.75 -2
5.7
0.30 25 2.20 -2
5.7 3.7
5.7 3.7 0.45 25 1.47 -2
* ( 4)
. 12 m-ClC 6H 4B(OH) 2 + Br g + H 0 > C 10 3 A = 2-10; CH C1COOH [fir~] =0.25
10 3B= 2.&-20 CHgClCOONa pH = 2-3 0.70 k AB/ [H+] 25 7 -6
(continued)
(Other catalysts see Suppl ementa]^y Table)
. 15 *>-BrC6H 4B(OH> 2+ Br 2 + H 20-* WAc20* 10 2A= 1; 10 3B= 8 NaBr 0.4 k AB 25 2.00 -3 ( 3)*
.16 w-IC0H 4B(OH) 2 + Br a + H gO *> WACZ)* 10 2A= 1; 10 3 B=8 NaBr 0.4 k AB 25 3.46 -4 f 1)
. 17 >-IC8H 4B(OH, 2 + Br8 + H 20-* WAc20* 10 2A= 1; 10 3B=8 NaBr 0.4 fe AB 25 2.41 -3 t 1)
SUPPLEMENTARY TABLE
Solvent HO
+ 5 vol % CH if0OH 10 3 A =2-10 10 3B =2-16
k = 3. 20 x io~ 2 + k l [catalyst]
o
00 CVJ 3
:* ** c-
O^O"* *H xf tO O
J
<*2
ID
O O t> O <D O> O) O "*& "*""* i
^rH <rH tO tO CD 00 |
TH 4) -rH Cvi CO <O -f-1 O
LO T-) ^H Os2 \7
%
M .
0) o
0
r-H
II
O cd
O 0
8
r)
0 O
O)
1 0 o
r1 iff
**
O
vH
0
O)
4-3 ^.
it
K
JO ^88
CO
GO a cb
CV? . <M
' 4-3*
cd
T* -tf W W CS2 tO
A cvj
9 ^ O -ii
0
ii
e ^ TH O 4J
o
X
O O
II >*
rH 9
CO r-H N ^* JL, 03
s o
o
t*a
5C
+
i
C\2
pq
cd
iz;
4-3
cd
o
r-H II ' '
bO
0) PQ eo co
o. C!
CD + 9 c5 +
Q. CO
ZD
CO g 3 S L '8
<1) 0 W CX
oq ..
$ PC;
** ..
4J>
O
fC
O5
jC
C G
O <U O tO
4-3 r-H > O
O 0 rH || || <
i o
6 CO d
^^ J
, . -a - pr; C\2
goo ^ o R o ^
4-3
g -g 8 rt V
<M o s n ^ |
!
Sd2ct ffi ^og ^ Catalys
atalyst eooT~iTHe9o ^ o ^
^ a"
CJ ^ *i ^
---!* C C S ^ *"*
g^ V oN ^ 1
i
0
""" 0 0 ^
CO
1
o
o
"co
I
Supplement 1955
>H
<D CD
CO
I
CH
O
33
a
O
bnseidrevtrievdes.
Reacosis
cto
bespeci
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rate Tetobablorefn.iantce
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VH
cd
0 CO
33
a
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CH CD
c CD CD
o
0
o
o
o iz;
o
cd 0
o
CQ
CO
rH
g
il oncentratlon.
o
d 0
CD
LU
2cd CO CD
CD
1 CC g
I CO co
ZD
d
33
O 1 CJ
CD
k
CH r>^l CH cd 0
LU CJ LU
r*4
d ""cd1 j
o
O PQ
s
0 CD 0 O
LO
.0 <n rH 03 CH
cc -a
CH
S
+
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<VH CD
cd o 0
LJJ
0 o h-
s
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4-3 0
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CD
1
cd
&
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cd
0 C!
e CD s _J cd
rH
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cd o CJ ^f 0 o rH O ^H N iH
rH o rH .rH co cd cd cd
a a -a 0 O rH rH rH rH
cd 4-3
s
CD rH 0 rH *H TH rH
8
0
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CD CD o CO (I d
^ 0 a
CO cd CD o a
4-5
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"cd 33
8 CD
4-3 4-3
CH o CH
OQ
CD
CJ rH
CJ o cd
S? o o C5 O
CH CO O 33 o CD
O X3 H
cd fcfl 4-3
4-5
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0 CJ cd CH
cd CD O CD CH
5
rH
CD 4-3
S o
C!
CD d CD
4-5 cd CD CD ^ ^
cd ii
a 0) pj 0
CD
CH CH Q) P> <D
CD CD 0 CD
x .0 a rH d TJ 0 d jlj
cd CD CD
d d S d CD
rH
j>
s
4-3 CJ 0 CO CO
CO CD
4-3
0
iH 6
CD CJ
J-J CO
d
fc.
4-3 O CD
CO cd 4-3 o II cd 0 rH CD
CH bO
.0 4i 4 0 CO W cd
5
0 rH
rH CD CH CD r|
rH CJ C O
<aj *d o o CH 0 0 CD X3
r-H rH rH 4-3 CD f^ X^ cd
CD
cd
a 4-5
CO CD CO
^ ^ gCH Q)
N'
CD
0)
CD CD 1 6
CO
5
40 rH
cd O cd 4-5 4-3
5 j h*> cd 4-3 CO
>
Q
CD o 4-3 cd
< g g d d cd 0 4-3
d
CJ
j^ flj CD o co
s
V) 0 rH
3 0
0
H
,0
d
CD
CO
CD
cd
OH a 4-3
CJ
0
o
i s
OJ CO CH
co
K*
CD rH o
5 o
a
j* CD
Scd CD rH
H-
1
4-5 4-3
H 01 w 1
cd 0 ^_l cd O
r-3 o2 ii CD 4-3 >-^ rH o rH
CO
3
O
SUPPLEMENT 1956
oT-
8 j n^.^ jo} i -j -- - r ,^ cT </r r .r CM ,r
Q)
siuaujujoo X- * * -x- * * * * x- * *
5 CD
e se 1 i
O- -- CO 9
-, C CO -*"
X
S
uq U C .
O -M OS O
o ^
to
...,,.. cu
w
8 1 8 8
0
S
O
Qjni'BJQdULO | LD
CV2
O
^
O
^5 s 9 s 9 9 9 9 s
2 2
MB 1 UO !}OB
SSBUJ pauj^aQ
PU3PPB ID ID LD LD LD ID ID LD ID
4.0 }unouiv
(}S K |B}.BO)
801 8CM 8CM 8CM 8CM 801 CM
8CM 8CM
US as as as as as as
- H- ,.
ID
0
LD
w
LD
Cv2 LD
O
CD*
ID
C\2 us S3
O "Jl O O CD 0 CD CD o O
<c + 0 II II O II M II
PQ
U II n II
PQ
II PQ PQ PQ PQ PQ PQ PQ
1 1 II
1 5
O CM
PQ LD LD PQ ID ID LD LD ID ID
|| 02 CV2 II CV2 W
4 II II II II II II II II II
CD CM CM CM CM CM CM CM CM CM
1> '-5s
LD
OO
CJ> O ID
O
O
O 0
O
0
O
O
0
O
o
O
O
0 0 o o o O
8* w
O
as w as as as as
SN
CM
11
o
fI
o
,1
o
ii
o a r1
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,i
o
PC
c:
<D
ffi
o O
CM
O
CM CM CM N O CM
CM 8 8 8 8 "CM 8 8
CM
8 CM
N
"c* "CM & "CM
"CM
"CM CM 8 25 25
25 25
25 "CM "CM "01 "CM "CM
01 as as
8 g" CM 25^,
O
CD
as
Reaot
oni +
s
*
on
W
CD
O 0 0
oCO
o
o
CD
if
as o
g
O 0
+ g" as
o 0
CO as
o o g
o
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f1 f t 09
T 09
f 09
f i 09
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L -f
as
1
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0
oc
C\3
in ffi 0
as
as
o
o
o 0 8. 1
PC
0
8^ o as 8,
o as
CD
asCO O
CD
as
9 CM o
o
g" gn
CD 0 0 0
O Kl O
g" o o o
s
tO O
a o as
as0 S o 0
o* & i. f i f 1 i
o
z ^ c. Kl
t LD *: 00 ^
Homogeneous Reaction Kinetics
332. 452
*
W) * =
'^ CO X 0
>+_ 0) Cti <D fe x io n CO 2
So 1 vent Amoun t of T3 W 0 -o E 3 6 D
--
C >, c
No. React i on 0) c * -o c 5 -H | 0 (d
T3 OJ <D 0 V-
(Med i urn) reactant -0 -M C 0> ^
<t <fl 11 5* CX 0
0 M- 0 E * n o
0) n) 0> 3: _j
f_
d
.14 * ()
m-GIC H COOH + HN_ >m-ClC H NH , N , C0 0 A= 2.5; B=0.25 H
y 290
o^ 4 1.5 40 733
64 3 6 4 2' 2' 2
CIHC:CCI 3
. 15 *t-BrC 0H 4COOH + HN Q >m-BrC 6H 4NH 2 , N 2, C0 2 / 2\
ciHc:cci 8 A= 2.5; B= 0.25 H 2^ 4 1.5 40 600 *
COMMENTS
Reaction. (.1) No appreciable decomposition of B during reaction time but ( *) observed unreliable results with substituted
benzole acid due to decomposition in H 280 4 solvent. Aniline sulfate is final product. ( 2) observed ratio of L/M = 0.70.
(.2) L/M = 0.53. (.3) No appreciable decomposition of B during reaction time. (.4) L/M = 0.88.
(.5) L/M = 0.81. (*6) L/M = 0.87. (.7) L/M = 0.86. (.8) L/M = 0.83. (.9) L/M = 0.71.
(.ID) L/M = 0.82. (.11) L/M = 0.71. (.12) L/M = 0.82. (.13) L/M =0.59. (. 14) (. 15) (. 16) L/M = 0.78.
CO
(.17) Reaction involves consecutive reactions. The first reaction forms an intermediate which reacts withasecond molecule
of B to form final products. Rate expression broken up into initial fe AB and following fc'iB rate laws. Where I represents
(X)
concentration of Intermediate.
Ob
to
Oi
LITERATURE
T. Bak, Acta. Chem. Scand. 1954, 8, 1733. ( 8) L. H. Briggs, J. W. Lyttleton, CSL 1943, 421.
k =
x I
So I vent Amoun t of Amount of
No. React ion Addend
(Medi urn) reactant addend
CO
COMMENTS
Reaction pseudo first order with respect to A. Second order constant calculated by dividing pseudo first order con CD
stant by calculated concentration of molecular 4. This was varied from 2.9 to 22 by adjusting the H 20 concentration.
Addition of NaH90 4 gave a very small salt effect.
LITERATURE
L.H. Sommer, W. P. Barle, J. Gould, ACS 1953, 75, 3765.
CO
CO X V k
r-1 tf cd L.
"o ^ 0 ^ e - k x ion
c |= Amount of -a -H T3 C
No. Reacti on > '-u c 0 O
<D reactant -a -o Q.
CO ^
X_^
-a -o H- 0 k
1 ^ 1 ^ Q
i n
CO
a
. 1 2-OH-3, 5-Br rtC H 0COOH + Br > 1, 3, 5-Br -2-HOC H + CO + HBr AcW 75* JD 3 A=5; 1D 3B = 4-8 HC104 0.10 feAB ao 5.8 -2
262 2 3 622
" 8 0.33 ao a. 55 -2
" 5 0.10 KC10 4 0.004 ao 5.6 -2 t?d
n 7 0.10 KBr 0.004 ao 4.7 -2
8 0.29 HBr 0.01 ao 1.35 -2
" 8 0.25 O.D5 ao 3.47 -3 CO
H 8 o.ao 0.1 ao 1.37 -3 OT
M 8 0. 10 0.2 ao 4.40 -4
" 8 0 0.3 ao 2.33 -4
" 4 0.10 LIBr 0. ID 33 4.9 -3
" 8 HBr 0.30 0 ao 2.33 -4
8 o.ao 0. ID ao 4.28 -4
" 8 0.10 o.ao ao 1.15 -3
ACW70* " 8 0.30 0 ao 1. IB -3
* V?
ACW 80* " 8 0.30 0 ao 2.93
.2 4-OH-3,5-Br 2C6H 2COOH + Br 2 > 1, 3, 5-Br a-4rHOC flH 2 + C0 g + HBr AcW 80* 10 3 A=5; 1D 3 B= 6 HC10 4 0. ID kAB ao 6.3 -1
" 4-8 0.10 LIBr 0, JO ao 1.30 -2
w 8 0.05 0. ID ao 3.4 -2
" 8 0.300 ao 3.00 -1
k =
Amount of
No. React i on
r e ac t an t
COMMENTS
LITERATURE
E. Grovenstein, U. V. Henderson, ACS 1956, 78, 569.
S^UdUJUIOQ * * *
^ tO tO Cv2
S o II s c CO
i
to
i 'oT
(L.
i i ' '
^ -M 9
^ o^ 0
w g
CD -H S ^ "J
O
E
<
9Jn,EJ8d.91 4^>
itn
MTJ | U O "1 }. OB CM CM OJ CM CM
PQ O PQ PQ PQ CQ
^ j j^
S SB Ul pQ U 1 J.9Q
^ S ^
I
S
s I
d S ctJ
o e
0
CO M
d co o
01
* C it o t-
PQ Z Q>
C " ^0 TD
W C-
o ? D O
o "*
E i_ , 0
0 C >*
o H r-l .
o o cvi
cd d CO CO TH
it ^H CD
< 3
cd
%H
bD
<C"
t*
^ s i
CO *J
-H
Ol OJ OJ
^ C
. <l> ^ o o o o ^ r-H CO "*-*
cu c
-0 * >-* ^10 ^o ^b ^te -H 4J O ^
2 0
S% r*1"! pr{ as mj S^ *H 0 IM O
li I OB ^ CO
0 O O O (0
r^
5
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a.
4-5
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^
o> cd ^-^ C
Z "O od h
LU ^ <: "
2 c ^ S
S a LU fi
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^} "^ ^ ""
co o o> J "^
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CD
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f-^
^
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W
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0> TH <rH
CO
^H
CO OC
T3 rj CD
CO OQ
W C8 o t, ?
CD O 0
r-H t
PC 3d ad 4- CO "^
O O O /"~V r
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Q.
0) 4- + + o-i ^ cB
CO C_, C-. t-i *C p?
co
c
PQ PQ PQ O ^-^ c
0 "" K* ac* x" o
ac <D o x~*
-fj
o o o o t-. "-* o
o N 01 0 pQ C
cd
8-
(0
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cc. + I
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CD
f-l
^ 06-^^0
S CD
s" t f t 1
0 ' ' ' L. ^
V_J t-l >^
* C* N 01 pQ
PQ CQ PQ 4- S &
4-4-4- >*
CM ^^ ^:
f-4 CO C3 CO *-
pq ^_^ ^.^ ^^^ JJH
CO CO CO O E
4- w m x '-
**-* *t *H H O* i
CO CO CO IT*
o as x PC o
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& CO
S o, .V
o to ** 1 S1 |
0
t^
m 0 0 -^ CQJ ^-^
o
0 *H Cj tO "* LO
SUPPLEMENT 1956
oj n}.Bje}. n
Q) C
~
S^UOIUJUOQ * * -X- *
o o
^ *:
- 3
si
1 1 1 1 1 1 1 1 1 1 1 i 1
x
f-4 -rH fcO CS2 -! CO C^
o o osc&WoWoco-tcD ^ o! o o
-W^^tO^-<CD-H-H - Tfl LO 02
O^ODQOQ^^Q LQ LO LO LO
9J n, BJ9d .91 Wc\2egWRFjcQtOC2 w C\2 CV2 05
MB | UO 1 }.OB m ' oi 1 CM 01 01 0)
<l o o
SSBUJ pQUt J-8Q - u5 L^
^^JJQOOQ^j"* -f
X
O ^TH^WWN^TH
. o
H-
rH T-t iH
O x,
H
10 LO
Q. + 8 00
odd
._ CM LO LO LO
CM 2 d do O 0 0
05 Z odd
C -f
O as II ^
x o
O O oS 0
05 c ^ ^
"^
r> A
'r
t>
-o k ' ci 1 801 0
Oj
0
Cfj
1 o* S XXX
01 01
V CM O
O O z
Z ffi
CV2 T-I ^)
LO
(D c d d d I LO LO
+ (d 4< LO LO
CM W
H
0 00 ? * *
O
0
(0
o PQ II H
. 00 CM PQ PQ
z 0 II 1!
Q 01 OJ
05 PS
Q. s- PQ PQ
(D o S LO* LO
c di do tb 0(2 dz
D 1! II II
0
E
d oo
C8 CM 0
JL d d
" I H- 9 S S
^ <; c)
}UOA |03 x x* 4 N x x x
-
a
React
on
\
T f i ?
S
01
55
Ci +
+
I s * *.g, ;.|
g
DC O
LO + g g 5CM +
CM
O
02
01
X
2:
O
oi na
01
Z
x
o
x
o
CO
+ x *Vi sC X 0 X O ^ *
0 CM o x c-> IZL o oo wo
o
ww c" ? 8 w 8 58
O *0
ro S S
a 8 * 8 w o w
s s s
O O O
* w"
u 3
d - tO ^ LO
Homogeneous Reaction Kinetics
332.901
COMMENTS
Reaction. (.1) Initial rate measured by ( 2) and rate constant calculated by dividing initial rate by total concentrations
of A and B. Increase In ionic strength from 0.50 to 1.50 depresses rate constant from 5.0 x if 4 to 3.5 x icf 4. Change in
buffer concentration from 0.25 to 0.75 had no effect on rate. Pseudo second order rate constant over reaction course
observed by ( 3). Third order constant calculated by dividing by concentration of nitrite ion. units, seconds converted
from original minutes. (.2) Third order rate law followed up to 20% reaction. Units, seconds converted from original
minutes. (.3) Reaction found to follow three different rate laws by (*): fe' = 2.0 x io~ 4 for k r [HOOCCH 2NH 3+]B 2; co
k = 4.3 for fegtHOOCCHgNH +]B[NO ""] and k AB 2. Each appeared to have some advantage at appropriate conditions, but no one
expression was valid over entire range studied by (*) .Units, seconds converted from original minutes. Negative salt effect
observed by ( 4) also rate depressed by H 280 4. Rate constant extrapolated to zero time as they decreased with course of
reaction. (.4) (.5) Rate constants extrapolated to zero time as they decreased with course of reaction, units seconds
converted from original minutes.
LITERATURE
(*) E. Abel, H. Schmid, W. Sldon, ZSC 1933, 39, 863. ( 2) J.H. Dusenbury, R.E. Powell, ACS 1951, 73, 3269.
( 3) T.W.J. Taylor, CBL 1928, 3099. ( 4) T.W.J. Taylor, OSL 1928, 1897. ( 5) T.W.J. Taylor, L. S. Price,
k =
Teremperatu k x Comments L
i
t
eratreu
Sol
vent Amount of Def i ned mass
No. React i on Addend PH
reac t an t ac t i o n 1 aw k n
CO
.5
.wX'-s- w ^x=, ,- 10 4A= 1.2-1.9 H/0 - 1 6.1 k A = -dA/dt 25 5.46 -4 *
(1)
X s HPO* fe= fe' + fc"[oH ] 25 1.10 -3
xzuzx 7. 1
Fe(CN) 6~ 3J 8.0 25 6.48 -3
9.0 25 5.72 -2
=NH4-{CJi ) NH (b)
1 10.1 25 1.24 0
1.11 4-1
O 11.1
12.0
25
25 7.76 +1
"I t
10 4A= 1.25 7.0 feA = -dA/dt 25 8.7 -4
.9 i W ^ PH ^PW IfPH 1 N2" ^^^ ^^ =NH "H
3 2 324 25 X X 2 25 5.5 -3 ('M 8) CO
HP0 4" [ 8.1
Fe(GN) 6- 3-) 8.9 fe=fe'+fe"[OH'] 25 3.3 -2
CH 3
10.1 25 8.5 -1
f ___ r I . ^N-X^==rN\-0
H 2 LCH 3 92N( 3} 2 4 2 6 N^ ___ / + 3 11.1 25 7.3 0
12.0 25 5.5 -Hi
i CH 3
8 fc'A = dL/dt 25 ~5 -4 * (}
.9.1 [CH 3 SC V
(calculated using
.9 and .2)
3
=0 +NH 3
fe =
-M * x ^ *
3 CO
c -M
0) Amount of Defined mass 3
CO c -H
No. Reacti on Addend PH t_ o 05
<D E
o reac tan t ac t i on law Q. aj
CO ^
E 0
<D n O
t _j
.9.2 =N(C 2H 8) [C 2H 44N(CH 3) SO^H,] + OH' > H 0 (calculated using 7-12 k"AB = dL/dt 25 6.0 +3 * f 1)
O . 9 and . 2)
CH
3
CO
CH
3
COMMENTS
CO
General. All reactions carried out at constant pH in presence of buffer, and in presence of excess K 3 Fe(CN)6 used to form A Oi
Oi
by oxidation of corresponding ^-phenol amine or -phenyl diamine. At higji pH the quinones produced may react further with
the K Fe(CN) . Reactions followed spectrophotometrically for dyes produced by a coupling reaction with a-napthol.
3 6
Reaction. (.4) Consists of parallel reactions (.4.1) and (.4.2) with consecutive reaction (.1) following (.4.2) .
(.4.1) (.4.2) Parallel reactions kinetically separated by following concentrations of the two dyes produced by coupling
reactions of:
(CHJ JJ=< > =NH and 0=1
o & ^^ ___ S^
with a-napthol. This combined with measured rate of (.1) allowed calculation of rate constant for (.4.2). Values for (.4.1)
were obtained by difference and give only order of magnitude. (.5) Consists of parallel reactions (.5.1) and (.5.2)
with consecutive reaction (.1) following (.5.2). (.5.1) (.5.3 Parallel reactions kinetically separated by following
the concentrations of the two dyes produced by coupling reactions of:
COMMENTS (continued)
with a-napthol. This combined with measured rate of (.1) allowed calculation of rate constant for (.5.2). Values for (.5.1)
were obtained by difference and give only order of magnitude. (.6) Consists of parallel reactions (.6.1) and (.6.2)
with consecutive reactions (.2) following (.6.2). Plot of log k/ kQ vs. JJL has slope = -1, see ( 2). (.6.1)(.6.2) Para
llel reactions kinetically separated by following the concentrations of the two dyes produced by coupling reactions of
This combined with measured rateof (.2) allowed calculations of rate constant for (.6.2). Values for (.6.1) were obtained r-i
by difference and give only order of magnitude. (.7) (.8) Non-linear dependence of log k with pH accounted for in
terms of rapid equilibrium between acid and basic forms of :
+ /\
and (CH SOjjNCgH ) (C 2H JN^/ \ =NH
\==/
R R Oi
with separate rate constants k 1 and k" respectively and equilibrium constant K. (.9) Consists of parallel reactions
(.9.1) and (.9.2) with consecutive reaction (.2) following (.9.2). Shown by ( 2) to be independent of ionic strength
(.9.1) (.9.2) Parallel reactions klnetically separated by following concentrations of the two dyes produced by coupling
reactions of : T T
__
S X
CH 3 CH 3
with a-napthol. This combined with measured rateof (.2) allowed calculation of rate constant for (.9.2). Values for (.9.1)
were obtained by difference and give only order of magnitude.
LITERATURE
f 1) L.K.J. Tong, J.P.C. 1954, 58, 1090. ( 2) L.K.J. Tong, M. C. Glesman, ACS 1956, 78, 5827.
CO k - A =
CO S
0 ^
rt (d 3 fe x 10 n ,4 x I0n CO
e -H
Amount of C
T> C L.
No. Reacti on So 1 vent Addend 9
5 ' O O
react ant C
o ^ Q. E
M- 0 E fe n ^ n
* <D a 0> s
K-
Q
.3 2,4,(N0 2) 2C6H 3030 2C6H 4-^GH 3 * 2 tH 8 (CH 2) 4NH -> CH 0OH fe AB 0 4.54 -2 *
0
COMMENTS
Pseudo first order rate constants observed as A in excess. Second order constant calculated by dividing pseudo first
order constant by initial concentration of A and multiplying by ratio of observed to theoretical yield of L. Competing
side reactions involving solvent probably responsible for low yields of L. (*1) In absence of &H 2 (CH g) 4ta 2 Cl" yield
only 25% which increased to 73% in presence of plperidine salt. (.2) Yield of L 92% in absence of CH 2 (CH 2) 4NH 2 Cl~
and 100% in presence of the piperidlne salt. (.3) Yieldof L 55% in absence of piperidine saltand58% in its presence.
r-J
I
I
CO
Ot
XJ
LITERATURE
J.F. Bunnett, E. W. Oarblsch, K.M. Prultt, ACS 1957, 79, 385.
0 0 0 0 0 0 0 O
a o
75 a a a 9. 8
"a o o
^ ^ a a a
*"*"* "*" 1
V o o o Ol 25 1i
*bs *%
as M i 25 25
H* 25
i
ii i
1
25 O
I 1
1 i 0 0
I i i O Ol
0 0 05 o
"a 03 "?. Ol
as i CM 0 0
01 f 0 "o O 6*
0 a 0
o
0
0
CM
as Ol
0 Ol
i 6"
o
o
a a to
0
a o
50
9 O o 0 a X
o 6" o as Ol p 3D
"a 0 0 3 0
"a a + CD
"O
Ol a a Ol o
*' o 25
u 0 0 o to ffi PL 3
(0 a 01 da
- f M O
01^ 0^ 01 R CD
25 25
x-x jj ,~-*. -f.
tt
25
p o O CD
0 25 p, o
0 -*K
as _^ *^** ft
H*
+
+
25 m
+ *
-j- ^^
ba (i) ?C
25
O 3T
CO >>
CD 2?
cr ni
o
o o
n
CD
O
CD
'a 'o "o
75 75 c^ 75 O 75 X
"a 5
Ol Ol
3
Mo Mo Mo Mo Mo
!
II ti II II II II II II n II
Vj V, v,
^
V, ^ ^J ^ ^ ^ ^J o
da da da da da da oa da da
n n II II H it n it n n
o 0 o o 0 o 0 o o
p 11
b b b b
CO K K s CO CO
Ol
3r *r 3r *r ar ?r ?r *r ^r s; PO >
Defined mass * P 3
H- O
fe 6 fe fe fe fe fe fe fe & action law fc-1
*
8 8 8 8 Temperature 1.
8 a a 8 8 a a
-* <cr
CO 9r o
CO 00 O Jfr'
5 b b b X
I
i 1 1 i i i i 1
"*, 05 o> 0)
a>
83 "
Ol I>J, ^
Z.Q6T XNS0LHQS
Homogeneous Reaction Kinetics
332.741
CO k =
0) k
cd (0
3
k x 10n
Amount of 6
Sol vent TJ C L.
No. Reaction 0 0 O
reactant o.
M^ 0 E fe n
<D O
Q
.11 CH CH CHBr + [CH CiOCHCH J"Na+ > C H J3:OCH(CH ) (C H ) -H NaBr (CgHg) 20 A= 1.7;B=0.09 te AB 30 3.4 -7
o <e DO * O DO 2537
.12 (CH 3) 2CHBr + [c^C'-OCHCgH^Na"4" ^C^CiOCHfC^) [cH(CH a> ^ + NaBr ( CA> 2 A= 1.7;B = 0.09 k AB 3D 1.5 -8
CO
COMMENTS XT
Second order rate constants calculated by dividing pseudo first order constant by concentration of A. Pseudo first
order constants increased about 30% during second half life except where a-hydrogen of ketone was substituted. Rate law
with respect to A not verified.
LITERATURE
a tO CD Oi C\2 lO tO CD LO tO
s -
II
I f
rfi
.a t>
c
* o
"v - to
^H
o
LO
<o
r4
o
<H
o
iH
tf3
O2
^- k. -H <D
rr4 tf CO CO 02 tO
CO LO O ^ CD CD ^
a w o
& >^ o
s 00 tO GO 00 Q Q <H
- i tO tO tO 02
1 1 1 1
X to o w 02
<tf u3 LO <-
o o
TH w z> -i
-I 02
o
i
oj
o
i
o5
o
i
w
o
i
w
o
i
c\2
o
i
to 10 Q to
i W oj
2 i
*B | uo i }. OB
3333333 3 3
SSBUJ POUIJ.OQ 4* ^ ^ ^e ^ j j -<* J
H- ^j
S J3 S 02 c3 S cS S o3
., J o o o o o o o 0 0
^ -!-
3
0 J
oq DQ pq pq pq CQ pq pq PQ
X
X ^ >- it n ii ii n ii ji II II
O
-H
c > 1 w N N > N
o
PC^ aw BBM WN WN a^ aaN
ft
H
O O O O O O C_>
S SI
CO CO
C
o
tf
LU 0) "a:
CD 0>
Z O ^
Z ^
^
QJ O
(D
O N
x
Q. x S
( +
rH
CO
09
'^W
0
-H
o
0 0, g
05
( Pt, bO bO HH tj) n c* "*Vi
o:
s s g> * g bO O
s S
H CO CO TH CO ^H
S t
^ x-v x p3 "^w pel **^o
s *" 5 S g S g W rH
f f T t M f
Sr_)
Q)
,
1
"
rH
>
F-i
S Q)
(-(
M a
f f
tt rH
S ^->
g gB S 8 B 8 g g ra cd
-H
CO
t^ tx< bu Q o pj pq pq g
CO CQ CO CO CO CO CO
01 n CQ n eo C9 09 n 09 C*
"j, "^w -^ ^ w ^ --*w
to -o g
S S g g g g g 5 d
0 ^ 02 tO ^f LO CO C^ CD 0&
z
Homogeneous Reaction Kinetics
332.744
A =
A x K
Amount of
No. Reaction Solvent
reactant
, 11 (C1GH 2) (CH 3) 2SiCl + CH 3MgI (CH 3) MglCl 5) 20 A=B^0.25 feAB 0-25 9.8 1.6
Co
13
COMMENTS
Rate law with respect to individual reactants not determined as A=B in all experiments. Second order rate law valid
until form at ion of second liquid phase at which point reaction rate observed to increase. At least one half life observed
before second phase appeared. Actual rate constants given by authors only for (.7). Valuesof E and A listed are not known
CO
as accurately as given in table. These were not rounded off so that rate constants between 0-25C may be calculated from them. Oi
LITERATURE
A. F. Reld, C.J. WilKins, OSL 1955, 4029.
OT k = A =
* i_ <p
* cti 3 k x I0n OT l_ CO
6 ,4 x 10n fJ 3 C3
Amount of J C
No. R eac t i on So 1 vent T3 C i_ Hal f-time O cd
0
0
reactan t C 0
._ +J Q. ^
6 k ,4 O
M- 0 <D n n O
03 J t _j
Q
. 1 (CHJ CHL 4- AgNO o > (CHJ 0CHNO o 4- Agl (15$ A= 0. 165; B = saturated 0 480 * ( 3)
32 2 322 'W 2
> (CHJ CHONO 4- Agl
3 A
CD
O1
O)
.2 n-C 4H v Br 4- A^I0 0 > A= 0. 25; B = saturated 0 1,250,000 *
(*)
^^^
~^ n-C 4H9N0 2, n-C4H9 ONO 4- AgBr
.4 (CHJ
> j_CBr 4- AgNO * > fV ^
P " n
u . ^/ ^ A= 0. 25; B= saturated 0 900 *
( 4)
252
> (CH ) CNO , (CHJ ,CONO 4- AgBr
33233
.4. 1 (CH 3) 3CBr + (CH 3) 4NNO a > CH gN0 2 A= 0.0 155; B= 0.032 feA 25 5.S7 -6 * ( x)
> (CHJ ,CN0 0 , (CHJ mNO + (CH ) NBr 45 5.24 -5
332 33 34 ft
63 2-90 -4 ,33.6 7 9
.4,2 PU
I\Ln f"1 U
^DT T-t /(L
\) n OT5r MWU
n N) XTMA -V
^ -6 f 1)
2 O 4 2
CH/0 2 A=0.020;B = 0.0048 kA 25 3.91 *
33
0.0306 25 5.56 -6
^ ( CH 3^ 3CN0 2' ( CH 3^ 3CON + ' G 2H 5 J 4NBl?
CO
.5 n-C 4Hg I + AgN0 2 >n-C H N02,n-C H ONO + Agl (cA) ao A= 0. 195; B^ saturated 0 5,700 * (*)
CH,ClN 0.16 0.64 0 600
O
/ p TT \ f
A= 0. 195; B= saturated 0 660 * ( 4)
.6 C 2H 5 (CH 3)CHI + AgW 2 > \ ^ " . / nJ
252
> C H_(CH J CHN0 0 + Agl ( 15%)
2 o o
>CH (OH CHONO -H Agl
A o o
co
Oi
2.5 x 10 6) * ( 4) Ob
.7 (CH g) 3 GCH 2I + Ag*0 2 > (c^ 8) 2o A = 0. 195; B= saturated 0 (t * 1= AAA
27 940, 000
^ v>ji
^ i/ po \/ PPU MA
v/L/n. _JNU ^ v>n
/\ PT4 ^/ PPH
^Ln OMH
uiNvj -f-
"^ A 0*7
-H-C>I
33 2T2 33 2 CH 3C|N A=0. 16; B= 0.64 0 5,800,000
^25 330,000
0 6,550 * (*)
.8 n-C H. I + AgNO n > (C aHB) 3 A= 0. 195; B= saturated
8 17 2
>n-C H, N0 o , n-C H ONO 4- Agl
8 17 2 8 17
(*)
A = 0 . 195; B = saturated 0 660 *
.9 (n-C6H 19 )(CH 3)CHI + A^10 2 > (^^ 2
> (n-C H.J (CHJCHNO, + Agl (22*)
613 3 *
^ (^-C flH , ,) (CHJ CHONO + Agl ( 16%)
oi3 y
( 3)
<W 30 A = 0. 165; B= saturated 0 292,000 *
. 10 C 2H 5OOC(CH 3)CHI + AgN0 2 >
>C H OOC(CH )CHN0 0 + Agl (80%)
25 3
>C H OOC(CH) CHONO + Agl
2 C 3
V) k
CO S o A =
0) R) u o
Amount of 6 - k x 10 A x ion 3
No, React i on "S cfl c
So 1 vent Hal f-time S 0) (0
>C DO
H CH *9ONO + AgBr (30%)
ess
. 14 -CH 3C 6H 4CH 8Br + AgN0 8 -* (C^),0 A= 0.05; B= saturated 0 60 C 4)
*
> ^~ CH 3 C 6H 4 CH 2N2 + AgBr (52%)
^-CH o C 6 H^CH.ONO
4 A
+ AgBr (48%) <0
CJT
. 15 p~Cn -OC_H -CH _Br ~t~ AgNO ^ <W A=0.05;B= saturated 0 very fast (4)
'3642 2 *
>^-CH 3OCAH 4CH 2N0 2 + AgBr (39%)
>-CH.OCAH
O O 4
CH_ONO
A
+ AgBr (61%)
.16 ^N0 2C6H 4CH 2Br ^ AgN0 2 > (C 2H 8) 20 A=0.05;B= saturated 0 10,800 (4)
*
-^^-N0 2CflH4CH 2N0 2 + AgBr (84%)
>-N0 2CAH 4CH 2ONO 4- AgBr (16%)
CODED SOLVENTS
Et 50* 50 vol % C 2H 5OH + H 20
I
CO 40 rH CO O
CD rH o rH od CD cd CO fn
g
40 CD CD
40 03 40
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40
0
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1 cd G 40
CO
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0. ft o cd 0 CD H
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co
CD
g
so
k - A =
<D
CO
3
k x 10 n ^ x io n 3
Amount of Defined m ass c
No, React ion Sol vent K5 " (0
<U
E
reactant act! on 1 aw
Q.
E
k n ^ n 8
\- J
.16 CH O0CH <60CH *i0Br + AgN0 00 C 2H 6OH 70 vol %-^H 20 A*0.1;B*0.14 k AB 64 4.30 -3 * (*)
k AB 6.44 -4 (1)
. 19 (CH 3) 2CHGH 2Br + AgN0 3 C 2H 5OH 70 V01 ^ + H 2 A^O.ISB^O.U 64 *
1.59 -5 * (1)
.20 (CHJ,CCH 9C1 -* AgNO. CgHgOH 70 VOl $ + H 20 A^O.SB^O.5 feAB 95
J O <6 O
1.01 -4 * (1)
.21 (CH.o ) aaCCH A9Br + AgNO o C 2H 5OH 70 VOl $ + H 20 A- 0.1^0. 14 fcAB 64
-5 ( 3)
.22 CH 2:CHCH 2C1 + AgN0 3 C 2H 5OH A = 0.5;B= 1.0 h AB 25 1.73 *
50 1.74 -4 18 1 8
i > | 0 C3 >- 2! 03 O
+ > (JQ w w
> 2: o o O
CO
0
CO
O O .' O 0 O O O O O O O O O
c
01 - 01 V 01 01 oi cr
o o o o o o ^o "o ^o ^o CO o o o
H. SC ffi K ffi 3
r-t-
i
n*
P C
3 r-
a <D
a
**
H- M
^ > II II II ^ ET II II >
II II O O O H P II II tl II 0 0 II 0) o
GO bd cn cn Cn ^ H- td tiJ to to ar en cn to E s
II II td to to " a p p '"*"
n n n n ^
w m n
II II M p*. "^ O
Cft H1- r^" -h
b b ^ ^ ^ b 0 0 0 O
p- t> b
000 <D 0 0
Cfi
i t i i i t O
D. o. o. ex o. p. P <3>
to td to td to td O -h
Sr ?r ^r ?r <0" jCr <O" u
D. D, O- O. P- P.
O CD
t1*" fe ?*" t1*" > > >
H II II II II Ii UJ UJ bJ UJ td td td
?r <Q a~ jsr <tr 3r 3
P P
S> >- > 1> > tE>
CO
& ba to bd bo CO
8 8 8 S 8 8 ro ro cn Temp eratu re
g 8 8 8 S cn cn o
01 w ^ ^ jvj ^ i-* t_. i_k cn Cn 03 Cn M.
to cn 03 o *r
H* CJ1 to O3 ^ 03
fO Go 5 cn Oi jo
X
i 1 1 1 1 i 1 It 1 I i I t
cn cn ^ A A CD -Q cn cs> CD CD 03 O3 Ol
f *
- 9 "*Q
11
-
****** * * * * * * * Comments
3 3 3> C- 3 3 3> 3 3 3 L i t eratu re
3s 3s 3
9561
Homogeneous Reaction Kinetics
332.751
COMMENTS
By Reference: ( 1) consider reactions may be partly heterogeneous at surface of precipitated silver halide but observe good
second order behavior from 5 to 50% reaction. ( 2) units converted to seconds from original minutes of authors, who
list values as 10 5 & which have been Interpreted to be ICf 5 x k. ( 3) carry out reaction in the dark: to prevent catalyti
tic action of precipitated silver halide.
Reaction: (.30) Twice authors value, who divided measured value of -dB/d by two. Second halogen considered to react
very much more rapidly than first. (.32) (.33) Identical product obtained from both reactions. (-34) Twice value
listed by authors. ( 2) divided measured value of -dB/dt by two as second halogen considered to react more rapidly.
(.35) Three times value listed by authors. ( 2) divided measured value of -dB/dt by three as second and third halogen
considered to react more rapidly.
(X)
CO
Oi
0}
LITERATURE
(*) I. Dostrovsky, E. D. Hughes, CSL 1946, 169. ( 2) M. Murafcaml, S. Oae, S. Tafceuchi,
Bull. Ohen. Soc. -Japan 1951, 24, 1. ( 3) S. Oae, C. A. Vander Werf, ACS 1953, 75, 2724.
CO k = A =
CO *
c 0)
fe x jQ n A x ion CO V-
-H 3
Amount of Amount of 51 c -H
No. Reaction So 1 vent Adden d -a c <D
03
reactan t addend c E 0)
. -M Q- 0 -H
*- 0
k n A n O
1
t
Q
CO
Na+ = B -4 (1)
.2 2-NO C H I + N " CH gOH A - B - 0.05 ftAB 132 9.6 *
264 3
150 3.35 -3
158 6.93 -3
166 1.05 -2 24.7 2 10
k = A =
ctf J k x 1 A x K
Amount of Amcu n t of e
No. Reacti on So I vent Addend
reac tant addend
.5 CH o0OH Na =B k AB SO 1.90
35 9. 13 Go
44 2.26
59 8.7 19.0 10
COMMENTS
Reaction. (.1) In absence of phenol reaction shows good second order behavior over course. In presence of phenol the
CO
concentration of phenol must be subtracted from aside concentration to give second order constant as well as a third Oi
Ob
order catalytic constant involving total phenol concentration. Variation of rate constant with initial concentration of B
assumed to be due to variation in siz-e of salt clusters. (.2) (.3) (.4) (.5) Rate law Is total second order but order
not determined with respect to A and B independently as A-B in all experiments.
LITERATURE
f 1) J. Miller, A.J. Parker, B. A. Bolto, ACS 1957, 79, 93. ( 2) C. G. Swain, M.M. Kreevoy, ACS 1955, 77, 1122.
NH
(A) (B) (L) (M)
0
k ~ <D
H- L. w L.
-H "-> 3 k x 10 n -H 3
c H
C
<o ^
3 Amount of C Def i nod mass 0
React! on L_ E U
No. Addend I 5 E
r e ac t an t ac ti on 1 aw Q. 0 +J
o J? O
CO ^ E " n
1 ? d> ^
h-
NH
COMMENTS CD
01
Reactions carried out under pressure slightly below critical temperature. For reactions above critical temperature of NH g 05
see 331.754. (.2) Rate law may require alteration after more complete study. Concentrations only estimated at reac
tion temperature. Formation of Br~ slightly ahead of guanidlne formation but results indicate only about 10% of carbon
tied up in form of intermediate. Addition of NaBr or KBr at 0.09M/1 increase yield in given time by a factor of about
four. BaBr 0* shows no effect. CaBr 2 decreases yield and ALBr 30 or BiBr o0 at 0.03 M/l show only slight increase in yield in
given time. (.3) All I~ appears in first ten minutes of reaction so that carbon Is predominantly in form of inter
mediate, Q. Concentration of Q = A-L/4. Authors show rate of appearance of guanidlne is first order with respect to con
centration of Q and first order with respect to effective L. Effective L is NH 4 I added + i[NH 4l] produced by intermediate
producing reaction. Rate laws may need to be revised on more complete study. Concentrations only estimated at reaction temperature.
LITERATURE
G. W. Watt, H. T. Halm, ACS 1955, 77, 312.
December, 1956
National Bureau of Standards- National Research Council
Homogeneous Heactiona EXCHANGE Liquid phase
332.761 Replacement of halogen by SJD
2 3
0) ,! =
c K -
V 1
l_ D
H * k x 10" A x 10n CO L.
3
Amount of Amo un t of 3
s- Def i ned mass c
No. (= Re ac t i on Addend A (0
So 1 v e n t E u
(D CO
J react ant ad den d act! on 1 aw i- E
o. r"' O
(D & n >4 n O
3 h- _J
CO
-3
( 21)
.36 .5 CaH 5l + 880 3= ( Na+) H 20 A- B = 0.01 feAB 25 1.92 *
35 6.5 -3
25 6.31 -4
37 1.94 -3 16.9 1.9 9
1.25 x 10~ 4 -4 ( 6)
Et49* 10 4A=4; JD 4B=8 CH COONa k AB 25 9.44 * CO
o
8 16 2.5 x ID" 4 25 9.05 -4
19 38 5.0 x ID" 4 25 8.29 -4
25 60 6.1 x ID" 4 25 7.73 -4
111 807 8.4 x ID" 4 25 6.54 -4
443 526 5.0 x ID" 3 25 5.73 -4
4-400 8-500 (1-50) x&~ 4 *A[S 20 3=] 25 1.02 -3
1.0 x ID" 4 -4 * ( 6)
.38 . 11 n-C3H7 Br + 1^8,0, Et49* 10 4A= 5; 10 3B= 1 CH COONa &AB 25 9.12
o
4.0 x ID" 4 -4 Oi
25 5 25 7.52 CD
443 53 5.0 x ID" 3 25 5.13 -4
&-400 1-50 (1-50) x 10"" 4 *AtS 20 3=] 25 1.02 -4
m~ 4 -4 * (")
.39 . 11 JLBr + MgS-0. Et49* 10 3A^2J 1D 3B=5 CH^COONa * ID
^A4 x fcAB 15 1.57
* o o
n-C 37
20 2.64 -4
25 4.50 -4
30 7.39 -4
35 11. 14 -4
n n H n k A[S 0 =] 15 3.35 -4
20 5.64 -4
25 9.62 -4
30 1.59 -3
35 2.41 -3 18.1 1.5 ID
1.8 -5 * C 6) ( 9)
.42 . 12 (GH O ) <C2CHBr + Na (C S i 0 O Et 49* 1D 5 A= 1; 1D 5B= 2 CH 3 COONa 1 x 10~ 5 k AB 25
2.5 x 10~ 5 25 2.5 -5
1 1
2 x 10~ 6 25 2.94 -5
0.5 1
1 x io" B * A '- S 23^ 25 5.0 ~~ o
1 2
2.5 x 10" 5 25 5.9 -5
1 1
25 6.2 -5 CO
0.5 1 2 x 10~ 6
Ol
25 7.2 -5 QD
(extrapolated to /JL - 0)
h AB 35 2.1 -3 * ( 81)
.43 . 13 EtW3* 10 2A = l;B > A
37 23
fe AB 35 1.3 -4 * ( ,i.
.44 . 14 (GH 3) 2CHI + SgO^ (Na+) EtW3* 10 2A = 1;B > A
k AB 12 1.32 -4 (1)
n-C 4He Br + S 20 3= (Na+) Et50* A = B = 0. 1 CHgCOONa 0.01
.45 -4
25 4.65
37 1.47 -3 16.9 1. 1 9
Alkenyl halide
12 9.32 -4
t 1)
Et 50* A = B = 0. 1 CH o0 OOONa 0.01 feAB
.46 CH 2:CHCH 2C1 + S 20 3~ (Na+) -3
25 2.51
7.33 _ t-f 14.5 1.2 8
37
5.3 -2 * (")
EtW3* 10 2A = UB > A feAB 15
.47 . 15 CH 2:CHCH 2I + S^O' (Na+) 1.4 -1
25
December, 1958
National Bureau of Standards - National Research Council
Homogeneous Reaction Kinetics
332.76 1
01
<D
k = A =
'ic 03
L. V)
a k x 10n A x I0n 3
<D Z Amount of Amount of Defined mass -H -H
cd
c
No. R eact i on So 1 vent <D aS
E rH Addend L. S L,
E
m reactant addend ac t i on 1 aw a> E 0
0.^ i- fc A O
n n O
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.48 C sH sOCH 2CH 2Br + S.0^ (Na+) Et50* A = B = 0. 1 CH COONa 0.01 k AB 37 3.44 -4 t 1)
3
50 1.16 -3
62 3.44 -3 19.0 8 9
GO
.49 CAOCH 2CH 2CH 2Br + S20 3= (Na+) Et50* A = B = 0. 1 CH n COONa 0.01 k AB 25 4.07 -4 c 1)
3
37 1.36 -3
50 4.04 -3 17.6 3 9
.50 C 2H 5OCH 2 CH 8CH 8CH 2Br + S 20 g= (Na+) EtSO* A = B = 0. 1 CH 3 COONa 0.01 k AB 25 7.26 -4 (')
37 2.35 -3
90 6.74 -3 17.0 2 9
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Homogeneous Reaction Kinetics
332.761
05 k =
C o ,4 = <D
t_ k x I0n CO l_
3 ,4 x 10n H
-H U
^
o i
z Amount of Amount of )ef i ned mass C -H
(U
No. Reac t i on So 1 v en t Addend L. (D 05
0 "LO (D E k_
re act an t addend acti on 1 aw E 0>
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340 25 1. 14 -2
680 25 1.25 -2
1,260 25 1.37 -2
680 25 1.30 -1
1,220 25 1.26 -1
-5 ( 16)
.62 (C00~) (CH )CHBr -t- S 0 = (Na4") H 20 10 3 A - 3-30; p. = 0.008 k AB 25 4.40
3 -5
10 3B = 7-70 0.03 25 6.25
0.06 25 7.2 -5
0.25 25 8.3 o
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0.09 25 3.0 -3
0.02 25 3.7 -3
0.005 25 3.6 -3
( 21)
K ^ 1:B >A fe AB 25 1.4 *
.64 .25 (C 2H 5OOC) (CH 3 )CHBr + S 20 g" (Na4") EtW3*
35 3.2 -3
-4 ( 21)
10^l;B>A feAB 35 8.5 *
.65 .26 (C 2H 5OOC) (C 2H 5)CHBr + S 20 3= (Na+) EtW3*
uo *i React
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Homogeneous Reaction Kinetics
332.761 ID
O) A =
c 0 k = C
L. (0 L.
3 fe x I0n j* x I0n 4-1 3
" d Amount of Amount of +J H
Defined mass d c
0 (0
No. E H
Reaction Sol vent Addend E E
^ in react an t addend act! on 1 aw Q. E -H
O
E fe A 0
ex ^ <O n n
I
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.76 C 6 H 5 CH 2CH S Bl' + S 23= (Na+) Et 50* A = B = 0. 1 CHCOONa 0.01 37 8.9
3
50 3.24 -3
62 8.5 -3 17.9 4 9
CO
4. 17 -4 i 1)
.77 C.H B ai > GH CH 8Br + S 83= < Na+> EtSO* A = B = 0. 1 CH 3 COONa 0.01 feAB 25
37 1.53 -3
50 4.65 -3 17.9 6 9 CO
= / ~K -3 ( l)
.78 Et90* A = B = 0. 1 CH 3 COONa 0.01 feAB 37 1.36
50 4.34 -3
62 1.28 -2 17.8 5 9
CO
O!
Sulfonyl-substituted alkyl (alkenyl) halides OD
25 7.22 -4 ( X)
.79 C 2H,SO aCH aCH 2Br + S20 3= (Na+) EtSO* A = B = 0. 1 ' CH 3COONa 0.01 feAB
37 2.60 -3
50 8. 1 -3 19.2 8 10
-3 (*)
.80 C aHa J|GH 8CH 8CH aBr + S20 g= (Na+) EtSO* A = B = 0.1 CH O COONa 0.01 feAB 25 3.58
37 1.23 -2
50 3.33 -2 17.2 1.4 10
-3 t 1)
.81 C 8H 6a0 2CH:CHCH 2Cl + 8.0,= (Na+) EtSO* A = B = 0. 1 CH d-COONa 0.01 feAB 12 1.71
25 5.36 -3
37 1.80 -2 15.8 2 9
37 3.76 -4
50 1.26 -3 18.3 3 9
EtW3* B > A 40 1.9 -5 * ( a>)
50 5.8 -5
.83 .7 CH C1CH I 4- SO =
22
(Na4 ) EtW3* B > A k AB 40 5.3 -5 * t 81)
23
a) 1.5 -4
.84 .8 CH 22 0 =
BrCH Br 4- S 23 (Na4") EtW3* B > A k AB 40 6.4 -3 * ( 81)
50 1.9 -2
.88 ClCH 2CH 2CH 2CH 2Br 4- S 20 g~ (Na+) Et 90* A = B = 0. 1 CH 0 COONa 0.01 ft AB 12 1.97 -4 (1)
3
25 7.34 -4
37 2.33 -3 16.6 1. 1 9
-3 f 1)
.89 eis-ClCH'CHCH Cl + S 0 = (Na4) Et 50* A = B = 0. 1 CH 30 COONa 0.01 ftAB 12 2.59
25 7.42 -3
#7 2.16 -2 14.4 3 8
k =
k x 10* A x
Amount of Amount of Def i ned mass
No. React!on Sol vent Addend
reac tan t addend act! on I aw
(Na4") -3
,91 0(CH 8 CH 2 C1) 2 H 20 ^O.02; E-0.05-0. 1 100
CODED SOLVENTS CO
COMMENTS I
Reaction: (.34) Units converted to M/l, sec. and natural logarithms from ml. of titrating solution, min. and base ID j
logarithms respectively. (.35) Rate constant converted to base e logarithms from base ID logarithms of authors and
from values in 1951 Edition of Tables. (.36) Rate constant converted to base e logarithms from base ID logarithms
of authors and from values in 1951 Edition of Tables. Values about 50< higher than values of ( 17 ). (-37) Values of
(*) of rate constants 30 to 40% higher than those of ( 1? ). ( 6 ) determine fraction of total thiosulfate present as S20 3
and find rate constant in terms of true [so =] is Independent of added salt, see (.38) (. 39) (.40) (.41). (.38) (.39)
2 o V-/J
(.40) (.41) Rate constant calculated on basis of total thiosulfate present decreases both with course of reaction, and
with Increase in concentration of salts. In terms of calculated [S rt0 ~] the rate constant Is independent of cation present.
2 *J
(.42) Data of ( 9 ) converted into terms of calculated concentration of [S 20 3~] by ( 6 ). (.43) (.44) (.47) (.51) (.52) Con
verted to base e logarithms from base ID logarithms of authors and from values In 1951 Edition of Tables. (.53) Con
verted to base e logarithms from base 10 logarithms of ( 21) and from assumed base 10 logarithms of ( 12). (.->4) (.55) Con
verted to base e logarithms from base 10 of authors and from values in 1951 Edition of Tables. (56) Reaction studied CO
by ( 8 ) with regard to pressure dependence from which they concluded the volume of the transition state to be smaller than
the volume of the reactants. ( 10 ) determined dependence with respect to ionic strength:
Give plot of data of many previous investigators. ( 12)( 13 ) determine temperature dependence of reaction. ( 14) studied
reaction over wide range of salt concentrations and observed a specific catalytic effect with LaCl g. Catalytic constant
for LaCl varied with concentration as did activation energy. ( 15)( 16 )( 17 ) studied effect on reaction of awide variety
3
of salts as well as other addends, log (fe/fc ) /%//T was not constant but observed to vary from 0.6 a.tjjl = 0.36 with K or
Na+ to 5.7 atyjT^ 0.08 with La4"^' Other addends included, urea, sucrose, glycerol and dloxane. ( 19 ) studied reaction
with respect to KNO , K SCK, K Co(CN) and found rate constant to be nearly the same for 0.034 salts even though /z varied
224-33
from 0.02 to 0.04. Rate constants of ( 21 ) converted to base e logarithm from base 10 of authors. Reaction also studied by
(23) (24) whose results agree well with those of later investigators. (.57) Values of ( 21) converted to base e loga-
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Li terature
3 3 3 3, 3
8G6T
Homogeneous Reaction Kinetics
332.763
A
Amount
of Def
i
edmasns Temperature R, X
ion A x 10n
Amo un t of addend acti
1onaw Cotsmmon L
i
terature
No. React i on Sol vent Addend
reactan t
n n
0.2 25 1.83 -2
0.05 35 5. ID -2
0. 1 35 4.84 -2
0.2 35 4.50 -2
0.05 Lid 0.03D 35 4.87 -2
0.05 0.033 35 4.78 -2
0.05 0.046 35 4.48 -2
0.05 0.068 35 4.35 -2
0.05 C H ONa 0.084 35 5.0 -2
6 5
0.05 42 8.94 -2 17 1 9
0. 1 42 8.84 -2 17.5 2 9
0.2 42 7.58 -2 16 9 8
w o
k = A =
L.
o
k x I0n ,4 x I0n m i_
o x ) td 3 +j D
Amo un t of E
NlO. React! on *-. c tf
c
So 1 vent Addend c- " "0 C S o nJ
L. i_
reactan t o C
E
5 ? E O
O 2 c ._ CL 0 -j
E k n A n o
< M- O
<D 5 f-V _J
Q
l> (8)
FCH I + C H S~ (Na4) 10 8A^1;10 8B^2.4 fe AB 0 4.79 -3
2 65 CH 3 OH *
30 9.64 -2 16.5 8 10
22 H S~
FCH S CH 2 CH <2 Br + C 60 (Na4") CH OH 10 2A= 1; 10 2B= 2.4 fe AB 0 1.86 -4 * (8)
3
29 5.26 -3 18.7 2 11
CO A =
H-
<n f fe =
fe x jDn A x 10 CO L.
e 3 -H
Amount of ^ 3
H ^ C
"0 C 05
No. R e ac t i o n So 1 vent Addend 0 o S 05
I 1 c J E
react ant E (D
C 0, fe ^
>4- O E n n
05 3
Q 1 -J
-4 * (8)
.24 BrCH 2CH 2CH 2Br + C^S" (Na4") CH 0OH 1D 2 A~ 14 B A feAB 0 5.78
H) 5.98 -3 18.7 5 11
(8) CO
10 8A-l;lD 2B^ 2.4 feAB 0 1. 12 -3 *
.25 FCH 2CH 2 CH 2I + C6H 5S" (Na+) GH if0OH
3D 1.04 -2 17.8 2 11
-3 * (8) 1
H S~ (Na4") CH OH 10 2A-1;10 2B>2.4 feAB 0 1.57
.28 0 CH 0CH T + G 65
C1CH 222
20 1.38 -2 17.4 1.3 11
(8) ID
feAB 0 2. 18 -3 *
.7 BrCHCH CH 0I H_S~
+ C Do (Na4") CH o0OH 1D 8 A~1;10 2B^.4
Si -2
20 1.91 17.4 2 11
-3 * ( 8)
(Na4") CH 3OH -A-*BA feAB 0 4.02
.28 ICH 2CH 2CH 2 I -H C6H 5 S~
20 3.62 -2 17.6 5 11
-3 * ( 8)
CH 0OH ^A^^B-3.4 feAB 0 2.39
.29 C1CH 2 (CH 2) 2CH 2I .+ C6H 5 S" (Na+) 0
3D 2.04 17.2 1.4 11
-3 * (8)
CHJDH M-x^^a* feAB 0 2.29
.3D C1CH 2 (CH 2) 3CH 2I + C6H 6 S~ (Na4") o
20 1.95 -2 17. 1 1.2 11
SOLVENTS
Et50 H 2
COMMENTS
Reaction: (.2) (-3) (.5) (.7) Structure presented for B is the enolate form favored by (*).
(.8) (.9) Reaction followed
to about 53%. Parallel solvolysis reaction probably negligible, see 212.471 (.193). Decrease of rate constants with Increase
In concentration of reactants is of the same order of magnitude as that caused by addition of a neutral salt. Plot of
log k values of ( 7 ) ( 9 ) versus 1/T gave a good straight line from which an average activation energy was determined.
(.11) Rate constant calculated on basis of second halogen reacting rapidly after replacement of first halogen. (.12) Rate 1
constant calculated on basis of only Br being replaced. (.13) Rate constant calculated on basis of second halogen
reacting rapidly after replacement of first halogen. (.14) Rate constant calculated on basis of second bromine co
C
reacting rapidly after replacement of first. Value tabulated is observed rate which is two times the value per halogen CD
of the authors. (.15) Rate constant calculated on basis of only iodine being replaced. (.16) (.17) Rate constant
calculated on basis of second halogen reacting rapidly after replacement of first halogen. (.18) Rate constant
calculated on basis of second iodine reacting rapidly after replacement of first. Value tabulated is observed rate which
Is two times the value per halogen listed by the authors. (.19) (.20) Rate constant calculated on the basis of only
bromine being replaced. Slight upward drift of rate constant, observed with chloride, eliminated by using excess alkyl
halide. (.21) Calculated second order rate constants drift upward due to participation of second bromine. Value
tabulated Is initial rate obtained by graphical extrapolation to zero time. (.22) (.23) Rate constant calculated on
the basis of only bromine being replaced. Second halogen probably contributes very slightly to overall rate constant.
(.25) Rate constant calculated on basis of only one bromine reacting as A in large excess. Values tabulated are observed
values, or two times the value per halogen listed by authors. (.25) (.26) (.27) Rate constant calculated on the basis
COMMENTS (continued)
of only iodine being replaced. Second halogen probably contributes very slightly to overall rate constant. (.28) Rate
constant calculated on basis of only one iodine reacting as A in large excess. Values tabulated are observed values, or
two tiroes the value per halogen listed by authors. (.29) (.30) Rate constant calculated on the basis of only iodine
being replaced. Second halogen probably contributes very slightly to overall rate constant. (.31) Pseudo first order
rate law with respect to A. Second order constant calculated by dividing by the C H ONa concentration. Authors postulate
5
reaction Involves direct elimination of HG1 follow by rapid addition to give the dithioalkenyl ether. High value of
"A-factor" probably indicates that this is not the complete rate equation. Reaction deviates from pseudo first order
behavior at low concentrations of B. (.33)
Spectropho tome trie method. "Infinity" samples indicated only 42$ of the co
theoretical amount of sulfide formed. (.34)
Value is the average between the spectrophotometrlc method (higher) and
analytical method for following reaction. "Infinity" samples Indicated only 69% of the theoretical amount of sulfide formed. <x>
i*
(.37) Value is a mean of results of ( 4)( 6). Spectropho tome trie method appears to give higher values.
LITERATURE
(*) S.F. Acree, G.H. Shadinger, ACJ 1908, 39, 226. ( 2) C. W.L. Bevan, J. Hirst, CSL 1956, 254. ( 3) J. F.
Bunnett, ACS 1957, 79, 5969. ( 4) J. F. Bunnett, G. T. Davis, ACS 1954, 76, 3011. ( 5) J. F. Bunnett, W. D. Merritt,
ACS 1957, 79, 5967. ( 6) J. F. Bunnett, R. F. Snipes, ACS 1955, 77, 5422. ( 7) J. Hine, W. H. Brader, ACS 1953,
75, 3964. (8) J. Hine, S.J. Ehrenson, W.H. Brader, ACS 1956, 78, 2282. (9 ) 0. R. Quayle, E. E. Royals, ACS 1942,
64, 226. ( 10 ) J.M. Rule, I.J. Wllk, T.I. Wrigley, W. G. Young, ACS 1957, 79, 6529. ( ll) W. E. Truce, M.M. Bouda-
kian, R.F. Heine, R.J. McManimie, ACS 1556, 78, 2743.
CO k = A =
w $ o <D
05 (tf u. w
E 3 k x ion A x io n 3
-M H
Amount of ((5
o c i_ S s a
No. Reacti on Sol vent <D 0 d>
i.
c .- E <D
reac tan t . -M Q.
^e 4 o -*-
H- O E n n o
0)
0) VO ( _J
O
(^)
.1 C 2H o Br + NaSCN 95% C 2H ROH A = 0.09;B = 0.2 k AB 25 1.67 -5
(')
95% CJi OH A = 0.09;B = 0.2 k AB 25 1. 15 -5
.2 n-C H 7 Br + NaSCN A 5
3
t 1)
A = 0.09;B = 0.2 feAB 25 1. 14 -5
.3 n-C 4Hg Br + NaSCN
( A)
95% C 2H 5OK A = 0.09;B = 0,2 Att 25 5 -7
.4 (CHJ CHCHBr + NaSCN
32 *
(1)
A = 0.09;B = 0.2 AjAB 25 1.20 -5
.5 n-C 0H 11 Br + NaSCN 95% C H 5OH
f 1)
A = 0.09;B = 0.2 k AB 25 7.3 -6
.6 (CHJ 0CHCH 0CHBr + NaSCN 95% C 2H 5OH
32 2 A
-5 f 1)
.7 95% C 0H OH A = 0.09;B =0.2 h AB 25 1.22
A O
n-C 6 H 13^Br + NaSCN
-5 f 1)
.8 + NaSCN 95% C 2H ROH A = 0.09;B = 0.2 AB 25 1.23
A
(CHJ 0CHCH 0CH A0CH 0Br
3 * A
( J)
A = 0.09;B = 0.2 k AB 25 1.24 -5
.9 n-C H, Br + NaSCN 95% C 2H 5OH
7 If)
t 1)
QCC OH
u _un A = 0.09;B = 0.2 feAB 25 1.27 -5
. 10 n-C H Br + NaSCN yo/b nk> _n
8 17 * 5
t 1)
QCC TI ATJ A = 0.09;B =0.2 feAB 25 1.23 -5
. 11 n-C 1QH 21Br + NaSCN y o~u pv- ori _u ri
CO
CO $ k A
6 T
aturemp
ree ion Co
tmmens
Amount of L
tetre
ratu
No. React! on So 1 vent S
0 0
re act ant c
H- 0
n n
Q
.12 n-C 16H 3gBr + NaSCN 95$ CgHgOH A = 0.09; B = 0.2 *AB 25 1.20 -5 ( x)
Aryl halide
COMMENTS
Reactions: (.13) (. 14) (.15) (.16) Produce in addition to thiocyanates, diarylsul fides and some disulfides.
LITERATURE
(*) T.I. Crowell, ACS 1953, 75, 6046. ( 2) J. Miller, A.J. Parker, B. A. Bolto, ACS 1957, 79, 93.
0) fe = A = 0
- , 1_ fe x lon A x lQn l_
SE ~^ 3 D
-H
C0 cd
Reaction So I vent Amount of reactant -o c 1_ S L.
No. <D 0 03 <D
c .- D- -M
E fe n ^ n
<D
'*o- z* h- -J
Q
CHgOH
feAB 35 7.2 -5 C 1)
.3 CH CH Br + S:C(NH 0)_ > CH CHSC(NH 0) ( :NH 0+) + Br"
32 A<b 3<
*AB 35 4.7 -5 C 1)
.4 CHgCH CH Br + S:C(UK^ > CH 3CH aCH 2SC(NH 2) (iNH^) + Br" CH QOH
o
feAB 35 1.40 -2 C 1)
.6 C H CH Br ^ S=C(NH ) "*-> C H CH SC (NH ) (:NH "*} *- Br" CH ROH
fe =
OT 5
A x iOn
E
No. React i on So 1 vent a c
c --
=4- O
BrC H -C=CH
6 4
.12 Br~
C 2H 5 OOCCH 2Br
CH 0 OH 3.0
o
I >
C SH O-C=CH <X>
JO
Oi
CO
COMMENTS
No measurable reaction observed with fully substituted thioureas. Reaction
(.9) addition of HO at 1 M or p-CEC H SO H
at 0.025 M caused no measurable change in rate of reaction. 2 3643
Addition of .007 M KBr may have increased rate slightly.
LITERATURE
C 1) R. G. Pearson, S. H. Langer, F. V. Williams, W.J. McGuire, ACS 1952, 74, 5130.
( 2) J.M. Rule, I.J. Wllk, T.I. Wriglely, W. G. Young, ACS 1957, 79, 6529.
06 00 ^-^ OD
1 -n- m-i
CO 01 go M
W CO *
^
S }. UOtUUJOQ
^3
I S9 s a
***
-^ X
^ 0 ^ W LO
2
to cr>
Ga
^ ^
O O 00 O
sjmr Tej9duis 1 Q CV ^f -^ ^H C\2 CQ tO *& "^"^
^H <N2 CO , ! !
r;V ; U O 1 5. OB
OQ PQ CQ
<C <$ <j;
SSBID D9UI.J.SQ
I
L.
PU9PPT9
PQ 35
CO 11 i! !!
U
o
-M -f
X
CO i X
f~
X
O. -f 0>
-o
*
-a v>
"cO
ULJ X
ft
x os
O
S uo 9 ^ ^
DC c
O QJ I LO tO tC c\i
X O>
0 1 }< S
O
11
CQ
i!
CQ
* r*** c
LU tan
react
u
o
n
of
t
Arn l| w W
CO X X CQ 9 ^<
-C
T~I r "^
X X
OS cd
cr
CD S
C3)
0
> 3
O <M 0
c:
^
s
5
" " 5
ion
React
i
rI 1
0 'HH
4- -f
^ f-.
CQ CQ
C9
0 oa g S
a to
CD
fl
K ON iS6i -
6u i ^uauja | ddng
<-i <XJ
o
Homogeneous Reaction Kinetics
332.771
o>
c m
<A X 0 k = A =
<a id c
c CO
93 z o -o E k x ion ,4 x I0n 3
Amount of Addend rt c
No. 8 S, R e ac 1 1 o n Sol vent -o c a)
0 O <D
g E
0- i re act ant (salt) I 1 c Q. E 4>
E O
4 <* o 0 k " o
<D (tf h- n n
CO O _J
.74 .2 CH g I + fir" ( 38 ) GO
H 2 A=0.06;B=0. 1 fc AB 30 2.69 -5 * ?=:
L = 0.06;M = 0. 15 35 1.35 -4
51 6.70 -4
67 2.41 -3 19.3 6 9
4 2 3.52 -3 (18)
32
n n 40 7.94 -3
ti n 50 2.07 -2 IB. 8 1.0 11
CO
4 2 Na+ or K+ = B 20 1. 18 -3 ( 18)(28)
n n -3 (18)
3D 3.28
n 40 8.90 -3 19.0 1.6 11
Na* R -2 (14)
4 3 64 6.9
n n K+ = B 64 4.8 -2
CO
-4 (30)
.78 caH 5i * cT (GH 8) 2CO 10 2A= 6; 10 2B= 3.2 L1C10 4 0. 11 k AB 14 1.40 *
25 4.30 -4
35 1.13 -3
46 2.75 -3
54 5.26 -3 17.0 1.3 9
= B -3 ( W)
.79 C2H 8I + Br- (CH 3) 2CO 10 2A= 4; 10 2B = 2.3 LI fe AB 16 6. 15 *
25 1.49 -2
32 3.02 -2
40 5.98 -2 17.7 1.3 11
K+ -6 (16)
.80 .7 n-C3H7 Cl + T (CH 3) 2CO A-^2; 10 2B= 1.5-2 feAB 30 4.8 *
(10)
0.2 4
- 50 2.8 -5
n n ... 60 4.6 -5 19
K^ -4 ( 16)
^2 1.5-2 60 1.08 20.4 3 9
50 1.92 -4
60 3. 10 -4 3D. 5 1.5 10
K+ -4 ( 18 )
~200 -2 60 7.3 22 2 11 CO
.86 -5 ( 30,
n-C 3H? I + Cl~ (CH 3) 2 CO 10 2 A~6; 10 2B = 3.2 L1C10 0. 11 fe AB 14 7.83 *
4
25 2.46 -4
35 6. 11 -4
46 1.64 -3
55 3.47 -3 17.0 6 8
Ll + = B ( 19 )
.89 (CH 3 ) 2 CHI + Br~ (CH 3) 2 00 10 2 A-4; 10 2B = 2.3 fc AB 40 1.71 -. *
50 4.38 -3
60 1.03 -2
2, 23 _o 18.5 1.6 10
70
60 6.5 -5 22 2
CO
.91 (CH ) 0CHCH Cl + Br~ An 90* L = M = 0.07 Ll+ =M f^J 1. 2 -6 (-)
32 2 k AB 69 *
55 9.70 -5
Oi
69 3.51 -4 2.0 Ob
ao.o 9
55 6.31 -6
69 2.49 -5 21.7 1.8 9
.97 (CH 3) 2CHCH 2Br * I" (CH 3 ) 2CO 10 2 A=4; 10 2B= 2 Li*, Na* or K4" = B feAB 40 3. 15 -4 * (")
50 8.44 -4
60 2. 16 -3 19.9 1.9 10
-dB/dt = B 2 -1 * ( aa)
.101 (CH J CBr -* IC1 cci 4 A=0.34; 10 3B= 2-10 25 2. 18
9 3
0. 17 -dB/dt = 1.43 dM/dt 25 1.82 -1
> (CH 3) 3CG1 + IBr -1
O UOD
C\Qf> 25 1. 15
^ (mi xed di ha) ides) 0.043 25 7.85 -2
0.022 25 3.70 -2
-5 * C 30 )
. 102 (GH 3) 2CHCH 2I + Cl" (CH 3 ) 200 10 2A=6; 10 2B= 3.2 LiC10 4 0.11 feAB 26 1.71
35 4. 16 -5
45 1.04 -4
55 2.58 -4
64 5.67 -4 17.8 2 8
ft A
ting
Supp of
Amount fined
Demass Teremperatu mments
CoI
1
No.
iemen 1951
actonaw
1
i A >< ^0
Am o u n t of Addend ad
dend -M
Cfl
No. React i on Sol vent S
reac tan t (salt) 0)
+J
n A n _J
K+ -5 (*)
10 2 A= 6; 10 2B= 2 R fe AB 25 7.3 *
. 116 (CH 3 ) 3 GCH 2CH 2Br + T (CH g) 2 CO
K+ -5 ( 10 ) Oi
= B fe AB 50 3.2 *
00 (CH_) 0 CO A = 0 . 2; 10 2 B = 4 Oi
. 117 n~ C 7 H l'5 C1 + l ~ o
60 7.8 -5 19
K+ = B -3 C 1)
10 2 A= 6; 10 2 B= 2 K AB 25 2.14
. 118 n-C7 H l5 Br+r (CH g) 2CO
K+ -3 (1)
10 2A- 6; 10 2B^ 2 = B ft AB 25 1.80
. 119 (CH 3) 3CCH 2 aH 2CH 2Br+r (CH,) 2CO
K+ -5 * (1 }
= B ft AB 50 3.5
. 120 .24 n-CH Cl + I~ (CH 3) 2CO A=0.2; 10 2B= 4
8 17 60 8.5 -5 19
K+ -6 *
( 10 )
= B k AB 60 1.7
.121 CH 3 (CH 2 ) li (CH 3 )CHC1 + l ~ (CH 3) 2CO A=0.2; 10 2B= 4
.25
K+ = B 50 3.0 -5 * <-,
A=0.2; 10 2 B = 4 /e AB
. 122 .26 n- C l 2H 2 5 C1 + r (CH 3) 2CO -5
60 6.4 17
,10,
K+ = B 50 2.5 ~o *
A=0.2; 10 2 B= 4 fe AB
. 123 .27 (CH 3) 2CO -5 19
60 6.2
R4 =B -5 (>>
. 124 .28 n-C H CI + I" (GHJ 2 CO A=0.2; 10 2B-4 fe AB 50 2.3 *
o
60 5.8 -5 19
. 126 K+ = B ( 43 >
CH 2CH 2CHBr + T (CH 3) 2 GO A=0. 18; 10 2B= 3.4 100 (no m easur able r<3 ac 1 1 cm)
CO
( 1? )
. 127 CH 2CH 2CH 2iHBr + i~ (GH 3) 2CO A=0. 13; 10 2B- 4 fe AB 73 3.08 -5 * rs-
80 5.84 -5
-4 ( 17 )( 48)
92 1.86 CO
-4 (")
99 3.58 Or
-4 0}
110 9.04 24.5 9 10
. 129 *" -B -6 ( 6)
J ^HCI + i~
in 2 (CH 23 (GH 3 ) 2CO AB 58 1.95 *
-5 ( 1? )
. 130 6H 2 (CH 2) 3CHBr + I (GHJ
o <;2 CO A = 0. 13; 10 2B= 4 k AB 36 7.39 *
-4 ( 1? )( 43 )
58 6.22
-3 ( 1? )
69 1.69
78 3.73 -3 20.4 2.0 10
05
C CO k - A = CD
H- CO $
+J ' L. ^o x ^n CO
o -a A x lDn -H 3
C E +J
QJ Z Amount of Addend "(0 C
-H CO 'u o
No. E p1 React ion So I vent c "a -o c S U
0 0 E 07
ir> O E
reactan t (salt) O <d c Q. k ^ n
M- 0 n
v cti i -J
3 (
CO o
Ll + -B ( 4 8)
. 132 & 2 (CH 2) 4 CHBr + Cl" An 90* A^B^0.07 t = fc AB; ^e = fe s 4- fe
<5 ' 3.69 U-6
>C H Cl + Br"
6 11 69 fe = 1.3 -6
"^ C O H .._ * rliir T* C,j_
s
-
k AB 73 6.98 -4 *
. 134 CH 2 (CH 2) 4 CHI + BF (CH 3) 2CO L = 0. 13; 10^= 4
89 2.86 -3
99 6.11 -3
110 1.45 -2 22. 1 6 10
A(~\ Q ft
- B feAB 40 8 . ou -7 *
. 135 CH 2 (CH 2) 4CHCH 2Br + Cl" An 90* A = B = 0.07 LI
55 4.84 -6
69 1.97 -5 22.3 3 9
h AD
w
n*~} 4.73 -5 *
A- 0.13; 10 2 B= 4 /? AB Of
. 136 CH 2 (CH 2) 5&iBr + I (CH 3) 2GO
48 1.43 -4
58 3.95 -4
73 1.53 -3 30.4 1. 1 10
K+ - B -5
. 143 HOCH 2 CH 2C1 + I" (CH 3 ) 2 CO A=0.2; 10 2 B= 4 fe AB 50 4.5 * (a3)
60 1.29 -4 22 6 10
K+ = B -5
. 144 HOCHCH CH Cl + l~ (GH 3) 2 CO A = 0.3 10 2 B= 4 k AB 35 1.02 * (8s>
45 3. 18 -5 22 4 10
<.
K+ = B ~1.2 -4
. 145 .4 GH 3OCH 2 C1 + l~ (CH 3 ) 2CO A=0.2; 10 2B= 4 fe AB 0 * (")
10 -3.9 -4
en 0>
c (0 $
k - A =
4- V, w
j rt k x ion
" d Amount of Addend 0 -o A x I0n c ^
-H C S <D
No. 6 r-t React i on So I ven t l- E L.
03 O
3 " (D E
r eactant (salt) O -H
CL A
E ko n n O
I S M- 0 <D _J
^ h
O
CO
K+ = B -5 *
( 48 )
. 146 CH o0OCH 0CH 0Br + i" (CH 3) aCO A- 0.2; 10 2B= 4 k AB 15 5.47
25 1.67 -4 19 1 10
B -7 ( 48 )
A- 0. 2; 10 2B= 4 ^ fc AB 35 9.8 *
. 147 C 2H 5OCH 2CH 2C1 + r (CH 3) 3CO
K+ -4 (*8 )
=B fe AB 25 1.6 *
. 148 (CH a) aCO A- 0.2; 10 2B- 4
CO
K+ ( 48j
n 15 4.80 -5 *
. 149 n-C H OCH CH Br + i" (CH ) CO A = 0 . 2; 10 2B = 4 k AB
49 22 -4
25 1. 46
35 3.82 -4 18.2 3 9
K+ -3 ( 12)
=B & AB 0 4.8 *
, 150 . 10 CH 3 OOCH 2C1 + I~ (CH^CO A=0.2; 10 2B = 4
CO
10 1.8 ~Z ao 5 13 Oi
K4 ~ R -5 l ) ( IS)
.151 (CH 3 ) 2CO A=0. 2; 10 2B= 4 k AB 25 6.0 ( ~
.9 C 2H 5OOCC1 + I"
K+ ( 36 )
- B -4 *
(CH a ) 2 CO 10 2A= 6; 10 2B= 1.5 fe AB 0 3.78
. 152 . 14 C 2 H .5OOCCH 2 Cl + 1" -3
20 3.25 1.9 10
l) I 1 l )( 12)
25 4.05 -3 (
ao 4
30 6.68 -3 17. 1 1.4 10
( 3 )
= B - 1 *
10 3A= 6; 10 3B= 5 ^ & AB 0 5. 34
. 153 C 0H OOCCH.Br + i" (CH 3) 2CO
<5 O 4 2. 27 0 11.5 9 8
SO
( 12)
K+ = B -4 *
A- 0.2; 10 2B= 4 k AB 25 2. 3
. 154 .6 NH.COCH Cl + I" (CHJCO
d <
2 30 3.8 -4
50 -3 18.3 6 9
2.53
O)
c CO k = A =
<f> IE 0
L. CO
o ^ (0 (0 3
t: * fe x iOn A x I0n 3
Amount of Addend +* s e Itf c
No. React? on Sol vent / *f T3 C S 0 cd
I -* E L.
to O 45 <D
.I irx react an t (salt) c Q.
E
I i fc A O ."^
0. %
<c E n n O
>+- 0
3 J
CO Q
K+ = B 50 4.26 -5 * <)
. 155 C 2H 5 CCH 2CH 2C1 "*" l~ (CH 3) 2CO A= 0.2; 10 2B= 4 fe AB
10 2 A= 6; 10 3 B= 5 K+ = B -4 * ( 36 >
.156 C H OOC(CH JCHBr + I~ (CH 3 ) 2CO k AB 0 8.22
< O O
3D 7.73 -3 17.8 1.5 11
K+ = B -5 (")
. 157 (CH 3) 2CO A=0.3^B=4 feAB 50 4.39 *
A-O.ftlD-B-4 K+ = B -5 f 11)
. 158 C 2H 5OOCCH 2 (CH 2) 2CH 2 C1 + T (CH 3) 2CO /5 AB 50 3.60 *
K+ = B 0 8.3 -3 * ( 12)
.161 .23 H OOC) 20CHC1 + I"
(G 25 (CH g) 2CO A = 0.2; 10 2B= 4 /8 AB
10 1.5 -2
K+ = B -5
. 175 CH 3 SCH 2CH 2CH 8C1 + i" (GH 3 ) 2GO A = 0 . 2; 10 2B == 4 /e AB 50 6.68 * ( 34)
60 1.52 -4 17
( 27 )
. 183 BrCH CH Br + l~ > (elimination see 422.477.1)
2 2
K+ = B -6 * (16)
. 135 CH on CHClCH <&0Cl + I" (CH 3) 2 CO A^2; 10 2 B= 1-4 k AB 60 9.9
80 5.42 -5 19 3 7
K+ = B k AB 0 2.28 -5
.1.86 ( CH ) , CO A=0. 2; 10 2B= 3.7 J (,
3 2
CH 2 : CHCH 2 Cl + I~
30 -4 * ( 22)(47)
0.2 4 iai ""
2 25 3.18 -4 15 1 7 ( )
0. 1
0.02 2 25 2.8 -3
K+ = B <1 -5 * (2^
. .187 CH CH'CHCl + I~ (CH i CO A- 0.2; 10 2B=^ 4 fe AB 30
3 3 2
K+ = B -1 (1)
CH : CHCH 2 Br + l~ (CH 3) 2CO 10 2 A= 1.5; 10 2 B= 1 /eAB 25 1.22
, 188
K+ -4 * ( 47 )
A - 0 . 2; 10 2B ^ 4 = B fe AB ao 3.41
. 189 CH 3 CH:CHCH 2 ci + i~ (CH 3 ) 02 CO
_
K+ -4 ^ (2
2) ( 47 )
A- 0.2; 10 SB- 4 = B ft AB 33 ^
. ISO CH :C(CH 3 )CH 2C1 + T (CH 3) 2CO
K+ n 1.4 -6 * ( )
CH ) 2CO R. AB 3D
. 19 \ CH :CH(CH)CHC1 + T
2 J 50 3. 1 -5 24 3 11
. 193 cis-CH 3CH:C(CH 3)CH 2Gl + I" A=0.2;10 2B-4 K+ = B -4 *( 24)( 4T)
(GH 3) 2CO kAB 20 7.4
. 194 K+ = B -3 ( 24)
3 32 (CH 3 ) 2 CO A= 0.2; 10 2B= 4 k AB 20 5.8
CO
Unsaturated alkynyl halide
^+
<&
. 196 (GHJ 0CC-GCH 0Br 4- i" (CH 3) 2CO 10 2 A= 1.5; 10 2B= 1 = B fe AB 25 8.7 -2 *
t 1)
O J * A
cs-
y 2 -4 ,16,
2-4 ao 3.39
0.2 4 5.0 -4 ( 10 )( 11)( 1 8)
25
-4 (* 4)
0. 16 3-4 25 5.8
0.08 3 25 1.0 -3
0.02 0.4 25 1.2 -2
00 2 2-4 -4 ( 18 >
30 9.5 __
-4 ( 10 ) ( 12 )
0.2 4 30 8.4
~
it ft 50 5.0 -3 18.3 1.3 10
8 25 2.43 -2
C H CH 0C1 + iBr
o o
K+ = B -4 (9a)
.301 0-CH C H CHC1 + I" (CH,) 2CO A=0. 1; 10 2B= 2 &AB 0 3.68
o 6 4 2
0.2 4 0 4.05 -4 CO
/8 AB 0 4.23 -2 (B)
.303 ^-GH 3C6H 4CH 2Br + I' (CH,) 2
K+ = B -5 * ( 18)
.304 .31 . C 65
H CH 2 CH 2, Cl + I" (CH,) 200 A=0.2; 10 2B=4 feAB 50 2.98
60 6.91 -5 18 4 7
Na+ = B -5 ( 9 ")
.305 C H (CHJCHC1 + I" (CH 3) 2CO 10 2A= 5;B=0. 1 ft AB 44 2.49
DO 3
K+ -5 (*)
A=0.2; 10 2B=4 = B kAB 50 4.56 *
.306 C6H 6 CH 2CH 2 CH 2C1 + r (CH,) 200
60 1.02 -4 17 3 7
K+ -3 ( 9 ")
A = 0.1; 10 2B= 2 = B fcAB 0 1.34
.307 %4r(cH,) BceH,CHBa + r (CH 3) 2CO
0 1.52 -3
0.2 4
K+ -3 ( a)
A=0. 1; 10 2B= 2 = B A! AB 0 6.00
.308 2,6-(CH 3) 2C6H 3CH 2Cl + T (CH 3) 2CO
N a+ -4 ( 9a)
10-A-ftB-O.l = B feAB 44 8.04
.309 O-CH C H (CH JCHC1 + I" (CH 3) 2CO
364 3
-5 ( 9 *)
Ha* = B feAB 44 6.07
.210 -CH C H (CHJCHCI + I~ (CH 3) 2CO 10 8 A= 5;B=0.1
o 6 4 J
C)
c
k A
1
Am
of
tonu 10 n cc
o z- Amount of Ad d en d I
addend Demasfineds actlawion T
eremp
ature .e x ion
No. c
Reac t i on So 1 vent ^ \
LO 6
react an t (salt) e
CL t? A o
3 n n
GO
.214 S,6-(CH 3 ) 2C' oH 3 (CH 3 )CHCl + T (CH 3 ) 2 CO 10A=.6;B = 0.1 Na+ = B -4 <9a)
k AB 44 2.75
0) k = A = <u
w $ 1-
o cO cd w 3
" ji 3 k x I0n A* x I0 n 4-1 -H
Amo un t of Addend "5 C
-M C
No. E ,H Reac t i on Sol vent "0 C
S o U
(D O E
- ^ r e ac tan t (sal t) I ^ C - i E
Q. O
Q. <c H- 0 e k n A n O _J
4) <0 v-
CO Q
33 1.06 -2 22 8 13
30 4.8 -2 18 4 11 CO
K
K+ ( 10 ) X*
.226 .51 0-C1C H CH Cl + I~ (CH g ) 2 CO A = 0 . 2; 10 2B = 4 - B /e AB 25 1.72 -3 * T3
64 4 c--^
30 2.80 -3 18 3 10 CO
= B -11 -5 *
( 2)( 3)
.227 m-CIC H (C H ) CHC1 + F~ SO 2 10 2 A^7; 10 3 A= 2.8 (CH 3 ) 4N+ ft A 2,38
64 65
8.7 -11 2.82 -5
19 -11 4.00 -5
25 -11 4.80 -5
90 -11 7.70 -5
5.7 (GH3)/-<cn 0.046 -11 7.50 -5
NH + = B -11 -5 *
( 2)( 3)
.228 fli-CIC H (C H )CHC1 + I" so 10 2 A^7; 10 3 B= 2.8 kA 4. 1
6465
6.8 -11 5.6 -5
K+ -4 ( 25 )
= B k AB 20 3. 16 *
.229 CH 2:C(Cr H fi ,CH 2 C1 + r (OH 3) a CO A = 0 . 2; 10 2B = 4
K+ ( 33 )
A=0.*10"B=4 = B ft AB 50 7.94 -6 *
. 230 C 6H 5 OCH 2 CH 2 C1 + r (CH 3) 2CO
60 2. 2 21 2 9
K" -5 (33)
= B k AB 50 4.44 *
.831 C 6 H 5OGH aCH aCH aCl + l" (CH 3) 2 t A = 0 . 2; 10 2B = 4
60 1.19 -4 21 7 9
. 252 K+ = B -4
(CH g) 2CO A=0. 1; 10 2B= 3. 1 k AB 0 3.06 C)
Nltrile substituted alkenyl halide
K4'
. &S CH 2: CC'lCHgCl + T (CH 3) 2 CO = B k AB ao 1.01 -4 * (22>
.;> cis-CHCi:OHCH 2 CL + r K+ = B -3 ( 2a>
(CH 8) 200 A = 0 . 2; 10 2B = 4 k AB 23 1.33 *
(low boiling isomer)
K+ = B -4 (22i
.258 CH g: CBrCHgCl + I~ (CH 3) 2CO A = 0 . 2; 10 VB -: 4 fe AB S3 1. 22 *
K+ = B rz
.259 cis-CHBr'CHCH-Cl + I~ (CH_) 2CO A = 0 . 2; 10 2B = 4 k AB 33 2.8 o * ( 83>
^ o d
.260 *+ = B -4 ( 23)
(CH g ) 2CO A=0.2; 1D 8B= 4 fe AB 33 1.6 *
en
c
*- * a; /e - j4 0)
V) CO
cti cd 3 k x I0n ^ x I0n
Amo un t of Ad den d C
E c
!- cd a> 00
R eac t ion So 1 vent c ^ "a c S E
No, o r"1 fl) O <u E V
re act an t (salt) o -S c 0 4-1
"a. as Q_ A
Q_ r~l E fe n n O
J M- O _J
Q K
CO
.263 / nrj \
\ v/n /
rY\
vAJ A=0.% 10 2B- 4
K+ = B fe AB 3D 4.6 -3 *
(M)
CHCl'CfCH oJCH *i CI + l~
K+ =B /eAB 3D 5 -3 * ( 22)
.265 ci + r (CH u ) <c CO A=0.2; 10 2B = 4
32
ci 2 c:c(CHJCH
Carboxy and halogen substituted alky halide
K+ = B fe AB 20 3. 1 -6 * ( 36)
.266 - I > (CH o ) CO A=0. 1; 1D 2B= 1.5
5
C 0H.OOCCHFC1
40 6.3 -5 27.5 1.0 15
C 2H 5OOCCHFI + Cl~
K+ ( J 8)
= B k AB 30 1.89 -5 *
.267 C 0H fJOOCCHCl 2 + I" > (CH 3) 2 CO A=0. 1; 10 2B= 1.5
40 2.2 -4 22.3 8 11
C H OOCCHC1I + Cl~
2 5
K+ _ c: * ( a0)
10 2 A= 6-; 10 2B= 1.5 .. k AB 0 9.22
.270 C 2H 5OOCCHBr 2 + I" ^ (CH 8) 2CO
20 1.12 19.8 7 11
C 2H 5OOCCHBrI~ -f Br~
_,.,.,...
O)
to
CO fe = A =
c
9
(0 CO L. 00 \-
" d o ^ e 3
fe x I0n ^ x I0n *-*
o> ^
Am o u n t of Addend C
No. Reac t i on Sol vent -o c (0
o o v_
tr> reactant (salt) c O
-M
- S^ 1 * 4- O
a.
n y|
n <si
3
0) <d 1 _J
Q H-
CO
.273 .41 A(CH 3)C6H 4N-GGH 2C1 + I" 10 2A= 2; 10 2B= 2 K+ =B -2 (**)
(CH 3) 2CO /e AB 25 6.95 *
2.5 1 25 2.54 -1 CO
1 2 25 7. 11 -1
'SOLVENTS
An90* (CHJ CO 90 vol % + H 00
( 45)
J
in H go
CO
COMMENTS CO
Cfc
Classification. f^
(.71) - (. 125) Saturated alkyl halldes (.197) - (.228) Aryl-substituted alkyl halide
(. 126) - (. 142) Saturated cyclo-alkyl halide (.229) Aryl- substituted alkenyl halide
(.143) - (.144) Hydroxy-substituted alkyl halide (.230) - (.236) Aryl alkoxy- substituted alkyl halide
( . 145) - ( . 149) Alkoxyl- substituted alkyl halide (.237) - (.240) Aryl oxo- substituted alkyl halide
(.150) Ke to- substituted alkyl halide (.241) - (.242) Aryl-carboxy substituted alkyl halide
(.151) - (.161) Carboxy- substituted alkyl halide (.243) - (.249) Aryl thio- substituted alkyl halide
(.162) - (.165) Carboxyl ate- substituted alkyl halide (.250) - (.252) Aryl sulfonyl- substituted alkyl halide
(.166) Nitrile-substituted alkyl halide (.253) Nitrile-substituted alkenyl halide
(.167) - (.173) Sllyl- substituted alkyl halide (.254) - (.265) Halogen- substituted alkenyl halide
(.174) - (.175) Alkyl thio- substituted alkyl halide (.266/ - (.271) Carboxy and halo gen- substituted
alkyl halide
(.176) - (. 185) Halogen-substituted alkyl halide
(. 186) - (.194) Unsaturated alkenyl halide (.272) - (.276) Benzimldazolyl-substltuted alkyl
halide
(.195) - (.196) Unsaturated alkynyl halide
COMMENTS (continued}
General. Halogen exchange reactions usually studied in Conments by Reaction. (.71) Rate law followed up to 70^
acetone as solvent using lithium, sodium or potassium salts. reaction wl th reverse reaction considered negligible. Nega-
When sodium or potassium iodide used insoluble chloride or i-ive salt effect. (.72) Rate of forward reaction
bromide separates and reaction goes to completion. When only. For simultaneous reverse reaction see (.74). (.73)
lithium salts are used reactions proceed to equilibrium and Addition of L1G10 4 eliminates drift in rate constants with
reverse reactions may be studied. Salt effects are observed course of reaction. Reverse reaction considered negligible. CO
and vary slightly with different halides. (.74) in H 20 reaction is in competition with hydrolysis
Comments by Literature References, ( 9 ) ( 10 ) ( 11) ( 12} Units and reverse reaction. In ethylene glycol solvolysls is
of rate constants converted to seconds and base e logarithms unimportant below 50C. Rate constants are for forward
from original hours and base 10. ( 13) ( 15) Units con reaction only. For competing reverse reaction see (.7).
verted to seconds from original hours. ( 20 ) ( 21) ( 22) In (GH 3 ) 2CO rate constants drift with progress of reaction.
K*.
Units converted to seconds and base e logarithms from origi This is attributed to greater retarding salt effect of Lil CO
nal hours and base 10. ( 23) ( 24 ) ( 25) ( sr> ) Units con than of the LiBr Initially present. (.75) Corrected
verted to seconds from original hours. ( 31)f 32) Units to base e logarithms from uncorrected values in 1951 edl-"
converted to seconds from original minutes. ( 33 )( 34) t.lori of Tables. (.70) Rate law followed up to 70*
( 35) Units converted to seconds arid base e logarithms from reaction with reverse reaction considered negligible. Nega
original hours and base 10. ( 36 ) ( 40 ) Units converted tive salt effect. (.77) Rate constant for forward
to seconds from original, hours. ( 41) ( 42) ( 43) Units reaction only. For competing reverse reaction see (.79).
converted to seconds from original minutes. ( 44) Units Only about 10% conversion at equilibrium. Negative salt
converted to seconds from original hours. ( 47 ) f 48 ) effect. (.78) in absence of added L1G10 rate con-
4
Units converted to seconds and base e logarithms from stants drift with course of reaction. Reverse reaction
original hours and base 10. ( 49 ) Units converted to considered negligible, see (.75). (-79) Hate constant
seconds from original minutes. for forward reaction only. For competing reverse reaction
COMMENTS C continued)
see (.77). Rate constants drift with course of reaction verse reaction see (.80). (.87) Rate constant for for
as Lil replaces LIBr. Values are calculated for rate near ward reaction only. For competing reverse reaction see (.83).
end of reaction as system approaches equilibrium. (.80) Calculated rate constants decrease with progress of reac
Rate constant for forward reaction only. For competing tion. This is attributed to a greater negative salt effect
reverse reaction see (.86). Corrected to base e logarithm of Lil than of LiBr. Value used Is that calculated for end
from uncorrected values in 1951 edition of Tables. (.81) of reaction as equilibrium is approached, (.88) Cal
Rate constant for forward reaction only. For competing
culated rate constants drift with course of reaction in
03
reverse reaction see (.88). Corrected to base e logarithm absence of added LiC10 4. Reverse reaction negligible, see
from uncorrected values in 1951 edition of Tables. (.82) (.81). (.89) Rate constant for forward reaction only.
Reaction followed to 70% completion and reverse reaction
For competing reverse reaction see (.85). Calculated rate
considered negligible. (.83) Selected data. Rate constants decrease with progress of reaction. This is attri
constant for forward reaction only. For competing reverse buted to a greater negative salt effect of Lil than of LiBr.
reaction see (.87). In presence of Ll"f" calculated rate
Value used is that calculated for end of reaction as equili
constants Increase with progress of reaction. This is attri Or
brium is approached. (.90) Corrected to base e logarithms
buted to a greater negative salt effectofLU than of LiBr. from uncorrected values in 1951 edition of Tables. (.91)
(.84) Reaction followed to 70% completion and reverse reac Approximate value giving order of magnitude only. Determined
tion considered negligible. Negative salt effect. (.85) .by getting best fltof data for reverse reaction. See (.96).
Rate constant for forward reaction only. For competing re (.92) (.93) Corrected to base e logarithms from uncorrected
verse reaction see (.89)- In presence of Li"7" calculated values in 1951 edition of Tables. (.94) Rate constant
rate constants increase with progress of reaction. This is for forward reaction only, but rate constant for reverse
attributed to a greater negative salt effect of Lil than of reaction not determined with precision. (.96) Reac
LiBr. (.86) Calculated rate constants drift with course tion followed up to 70% completion in (CHJ CO, and reverse
O fi
of reaction in absence of added LiClO . For competing re- reaction, (.91), considered negligible by ( 29 ). Negative
d o
00
g constants |
ate
|
AH
Calcula.ted
|
CO
reasaction |
| Cotor ected | wicoutrhse |
edition |
1951 loegarithms rerseaction
|
CD
reverse |
ting
| retarding
11 negligible. ributed
tto
reaction
/ard
O
S 40
o
d
CD
0
0
CD
CO apnroaches
CQ
f-t CD
5 CD
40
cd
<M
0
0
G
r-H rH
d CD
0
I |
O
CO CD G
CD CD CD CD 40 G {-, cd CD
0
cd
C o G ecrease CO
cd
rH CX cd
I
CD
,0 0 o CO
PQ 40
CO
0 05 d X3 CD ,G rH
CD
iH
I
"i*"*" a
CD 40 .0 Cti rH O 40 G ,-3
40
O G CO
o 40 O iH 3 0
cd
CD CD 40 d 0
73 G O
40 CO AH
cu AH
d 40
S
A-H CD rH TH
A^ cd Jr
S a
O AH 40 O rg
4O CO CD 0
AH
CD
40
0 AH
CD o
0
3 g
CO CD
nstan G CO
d d tants 0 0 G 40 AH rH
CD
0
A
40
0 AH 40
d
b
0 CD CD
rH
oj 4J d
CD
g 40 s~\
&
3
CD CD TH rH CD
40 CO 40 40 40 %
0 cd 0 o CD 0
o rH o rI
G rH
f
CD O 0 0
40 o AH
ergfaetictve at
efLi]
of
nesalt lcreaculated
aend
cof
cd 0 O dernNeegslgieaidtbilve. 40
eseeavcetirosen with
rig
(.
109)
OS For ncsrteanhste
remvpertsieng dcwioepro
coreac O lcuelas.ted
acons
ablCrate ncoruecested
valed
uIn
1951 Nseeegatlvesalt
:lon
(.
ill). wiof
drift vcteirosne.
Reea9
,sprerotghre.s rconsi progres
asereact
of
neautgeaatetdievre
ibgrto
e
r-l
aep3mquriolabcrihuems.
i
40 CD
03
S o
8 40 TH 40
S
0
40
s
A-H
CO
"ta*- 40
TH
d
d
s
CO FH CO
0 G
CD AH 0
CO 0 0
.3 CD
continued)
rH
g
,H CD
CD
CD
,3
&
bO
rH
0
AH
0
AH
rH
0
r-H 0 TH PS rH
.0 rH 40 40
rH 1
| S g
a
bO CD rH TH
A f-j rH
v_ CD 40 CD o CO co o rH H TH cd rH
rH JU3 40 OP CO CO cd G G O H 40 oCD CD
g
cd
p. d
CD 40 A-) rH CD 0 0 CD CD 40 CD CO
G
G 0 g cd ,0 0 O AH PS o o (H (H CO HH bO iH CD
LU
0
AH
G
11 h
i
CD CD
PS CD
rH CO
40 AH
o CD G
rH
CO cd
f
G 40 rH CJ
O
O
fcloenrcwstaeedn.rdt
SedatRatfor
rH pq
7340
(-91).
(-97)
1 40 Q
CD
lnoesucelsrnatecaendste of
cparate
of
In cirwith aertto
rpis
This agitbreounattse.der lar.ested
ogrcrnega-
CO H cB
1 cat
and
ntsalt
oefto
aof bftrauenitioectndc b"
ireaon/^ 0
1oto
only
25%
ftlon moasrwpmletdeiodn
oIn
clfIlater driloof
Carate
1 cwith dre.sorend
bLiResrceovaCnsceit104
added
of
crnupeslratocfengtdirtsoesn aIn
1atvipcoe03).tnirosneg Li* riencaldoicmstiepanodtinogn
cwith
40
40
rt
rH
1 atvpcireotdinoseng
ecroawemcsee
For
froonly. 1ec(.aorecmsee
For
ronly. 1 LlValcfaelareBcuct
efthan
of
salt
Lil
tive G
0
0
40
G
1ailin
with
crate
of roncenuasrlitseaneidsatel enotve9rmol3aievtneionsg
Ratdi=fstep
0.cr
wher
ft.
| 2 agoectnrexasitmporahniep.itecsodal -
rRatecdby
1
H
3 foabh1ges.uramtyl02)edne.
i(.disalso
stSome
1
i
CD CD 1C
40 H AH to
1 m1gfea01)oetcti.ve.
zerReac-
t(.Neefisalt
tion
S
rH
S O O
G o g
X O rH
e
f
CD TH CD 40
Si C\2 40 a)
r-H
TH
40 o
40
CO 05 CD
d CD a O
1 AH
o
CD
G
g
TH
0
d bO CD
s" g s
O
CO O 40
rH
TH
0 d
CD rH
G
rH
II
40 0
40 cd
d
rH rI
rf*- t,
g d S
s
G
0 bC B" d
o 0
CD g rH CD
40
73
TH
O 40 oCO O
CD
" rH
TH
AH 40 rH
C AH H CD rH O
O CD G AH
bO
g
40
73CO AH
tn
0
AH
O
G
40
H
40
I
Homogeneous Reaction Kinetics
332.771 31
COMMENTS (continued)
(.123) (.124) (.125) Converted to base e logarithms from un- stant for forward reaction only. For competing reverse reac
corrected values in 1951 edition of Tables. (.127) Rate tion see (.138). (.140) (.141) Forward and reverse
constant for forward reaction only. For competing reverse reactions. Actual rate constants not given only activation
reaction see (.128). (.128) Rate constant for forward energies and frequency term for (.140). (.145) (.150)
reaction only. For competing reverse reaction see (.127). Converted to base e logarithms from uncorrected value in
(.129) Reaction followed only to 27^ completion as faint 1951 edition of Tables. (.151) (.152) Converted to
iodine coloration appears at this point. Calculated rate base e logarithms from uncorrected value in 1951 edition of Co
constants decrease about 4% in this range. (.130) Rate Tables. Calculated rate constants decrease with progress of
constant for forward reaction only. For competing reverse reaction. (.154) Converted to base e logarithms from
Ob
reaction see (. 131). (.131) Rate constant for forward uncorrected value in 1951 edition of Tables. (.155)
reaction only. For competing reverse reaction see (.130). Calculated rate constants decrease with course of reaction.
(. 133) Rate constant for forward reaction only. For competing (.156) Reaction followed to only 35% completion due to
reverse reaction see (.134). Someparallel elimination reac subsequent decomposition of iodoester. (.157) (.158)
Cr?
Oi
tion noted by ( 1). (.134) Rate constant for forward Calculated rate constants decrease with course of reaction.
reaction only. For competing reverse reaction see (.133) . (.150) Rate constant for forward reaction only. Accompanied
(.135) Rate constant for forward reaction only. Corrected by parallel elimination and racemizatlon reactions see
422.471 and 112.470. For reverse reaction see (.160).
for reverse reaction but rate constant for reverse reaction
not given. (.136) Rate constant for forward reaction (.160) Rate constant for forward reaction only. Accompanied
only. For competing re verse reaction see (.137). (.137) by parallel elimination and racemlzation reactions see 422.471
and 112.470. For reverse reaction see (.159). (.161)
Rate constant for forward reaction only. For competing re
verse reaction see (.136). (.138) Rate constant gives (.162) (.166) Converted to base e logarithms from uncor
rected value in 1951 edition of Tables. (.169) Slight
order of magnitude only. Determined by obtaining best fit
(.139) Rate con- negative salt effect. (.176) (.180) Actual rate of ex-
for data of reverse reaction (.139).
December, 1956
National Bureau of Standards - National Research Council
Homogeneous Reaction Kinetics
332.771 32
COMMENTS (continued)
change is tabulated rather than half rate, (per halogen), value in 1951 edition of Tables. (.223) (.234) Rate
listed by t 28 ). (.184) (.185) Some iodine is also constants for the forward reaction only. For competing re
liberated during reaction. (.187) No measurable reac verse reaction see (.25). Authors consider total reaction
tion after six hours. (.192) Rate constants decrease to be best expressed as the sum of the parallel reactions
with progress of reaction. Value is average for first 40<? (.2?) and (.224) Involving Br" and the ion Pair Br"Ll^
reaction rather than average of all values by ( 21 ). respectively, (.225) Rate constant for forward reac
CO
(.196) Hate constants calculated, graphically but decrease tion only. For competing reverse reaction see (.223) (.224).
with course observed as first and last points fell below (.226) Converted to bas>3 e logarithms from uucorrected
authors straight line. (.197) Converted to base e value in 1951 edition of Tables. (.227) (.228) Cal
logarithms from uncorrected values in 1951 edition of Tables. culated rate constants decrease with course of reaction.
Addition of H,0 observed by ( 44 ) to cause decrease in reac Value tabulated is that extrapolated to aero time. (.237)
tion rate. Values from 0.09 to 21% by weight of water are (.238) Converted to base e logarithms from uncorrected
given. (.198) (.200) Third order rate constant cal value in 1951 edition of Tables. Calculated rate constants
Oi
culated by dividing pseudo second order constant by concen decrease with course of reaction. (.240) Converted to
tration of A. Reaction performed in the dark to avoid halo- base e logarithms from uncorrected value in 1951 edition of
genatlon. At concentrations of A and B > 1 M/l react! on much Tables. (.241) (.242) Rate constants of these opposing
faster and some halogenation of benzene ring occurs. reactions calculated from analysis of polarlmetric data
(.211) (.219) Calculated rate constants decrease with course involving simultaneous, exchange racemizatlon and solvolysis
of reaction. (.221) First order rate law valid for reactions. See 112.470 and 212.471. (.250) No measur
first 40% reaction only. Beyond this r^te drops to less than able reaction in 10 weeks, (.251) Calculated rate
1% of initial rate when 5D% of whichever reactant was In lower constants increase 15% In first 45% reaction. (.255)
concentration is consumed. This is not an equilibrium effect* (.256) (.257) (.258) Only allyl halogen assumed to react, as
(.222) Converted to base e logarithms from uncorrected CH 3 CH-CHC3 gives no measurable exchange in 8 hr. See
COMMENTS (continued)
(.187). (.259) Reaction studied in mixture containing of iodoester. (.268) Reaction followed to 60%. Subse
95$ els- and 5% trans-lsomer. Rate constant extrapolated quent decomposition of iodoester occurs. Negative test for
to 100% cls-isomer. (.260) Reaction studied In mixture F~. (.269) (.270) Reaction followed to only 35% due to
contalning75% trans-lsomer and 25% cls-isomer. Rate constant subsequent decomposition of iodoester. (.271) Reaction
extrapolated to 100% trans-lsomer. (.261) (.262) Only followed to only 35% due to subsequent decomposition of iodo
allyl halogen assumed to react, as CH 3 CH'CHC1 gives no ester. Negative test for F~. (.272) Formula corrected
measurable exchange in 8 hours. See (. 187). (.263) from incorrect structure given In 1951 edition of Tables. Co
(.264) (.263) Calculated rate constants decrease with course (.273) Rate constants corrected by power of ten from values
of reaction. Only allyl halogen assumed to react. See {. 187). listed in 1951 edition of Tables. (.274) (.275) (.276)
(.266) Reaction followed to only about 20% due to subsequent Formula corrected from incorrect structure given In 1951
decomposition of lodoester. Negative test for F~. (.267) edition of Tables.
Reaction followed to only 35%due to subsequent decomposition
<0
LITERATURE
(*) P.D. Bartlett, L.J. Rosen, ACS 1942, 64, 543. ( 2) L. C. Bateman, E. D. Hughes, C.K. Ingold, CSL 1940, 1011.
( 3) L.C.- Bateman, E. D. Hughes, C.K. Ingold, CSL 1940, 1017. ( 4) O.M. Bennett, W. A. Berry, CSL 1927, 1676. ( 5) C.W.L.
Bevan, E.D. Hughes, C.K. Ingold, Nature 1953, 171, 301. ( 6) F. G. Bordwell, G. D. Cooper, ACS 1.951, 73, 5184.
( 7) S. D. Bowers, J.M. Sturtevant, ACS 1955, 77, 4903. (8) C. A. Bunton, C.H. Greenstreet, E.D. Hughes, C.K. Ingold,
CSL 1954, 642. (9 ) G. Chambers, A. R. Ubbelohde, CSL 1955, 285. ( 9a) J. C. Charlton, E.D. Hughes, CSL 1956, 855.
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i 1 1 1 1 1 1 1 1 Amount of
Q, p, P> p, p. P. P< P. P
adden d
n-n-rt-n-c-+-n-ri- n- ri
ll II II II II M II II "
Defined mass-
act I on 1 aw
^bdbdbdbotdbd od ^
I , |
Tempe rat u re
03 0 6 0 0 aS ^oq0q
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Comments
L i teratu re
Homogeneous Reaction Kinetics
352.750
0) C
L. k = A = CO 3
t> -o -H
-H LO .A* x-* 10 n -M
Amount of E C
No. ri cd
React! on Sol vent Addend -o c E 0) t-
reactant E 0
o> E +J
Q. k ^
1jjl* E n n O
0 O -J
h-
Q
.9 [(CH ) CHO] OPC1 + 2(n-C H ) NH > (cant.) C 2H 5H 10 2A =5; B = 0.1 -cU/ dt = feAB 25 5.5 -3
32 2 492
40 1.03 -2
2 0.05 NaCIO 0.2 25 2 -2
4
2 0.1 0.2 25 7 -2
4 0.1 L 0.04 25 8 -3
4 0.1 M 0.12 25 1.5 -2
.10 [(CH ) CHO] OPCl + 2[C H (CH )CH] NH > C H -dA/dt~ kAB 40 1 -5
322 2032 6 6
64 -5
(products not
.11 [(CH3 ) 2 CHO] 2 OPC1 + (C H ) N > determined but C 6H6 feAB 0 5 -5
on ly one mo 1 e
of amlne con
sumed. )
LITERATURE
I. Dostrovsky, M. Halmann, CSL 1953, 511.
o -a k x A x 10
Amount of
No. React!on So I vent Addend
reactant
.1 (CH 0) OPC1 + F~ (CH 0) OFF + Cl" C 2H 5OH feAB 0 (too fast to measure)
3 2 3 2
=B feAB 0 2.8 -1
.2 (C H 0) OPC1 + F" (C H 0) OFF + Cl" C 2H 5H
252 252
Cl" =B -2
.3 C 2H 5OH 10 3 A = 5-14; feAB 0 3.0
10 *B = 3-23 25 2.3 -1 13
13 -2
60% C H OH + H 0 25 3.9
25 2
COMMENTS
Reaction: (.2) Value of rate constant approximate as reaction almost too fast to measure, (.3) Value of rate constant In
60% C 2 H 5 OH solution corrected for parallel solvolysls reaction see 252.570.
LITERATURE
December, 1959
National Bureau of Standards - National Research Council
HomogtntouB Ructions ELIMINATION Liquid phase
402.450 Hydrogen ion elimination from CH bond activated Amounts are in M/ I.
Rate constants are in
by adjacent CO, (COOR), (CN), NO,
M/ I and sec.
-C-H + B BFT *
I Coded solvents at end
Reaction types:
I of Table.
C-H + B -fc- -f- BH
01
c V) <D k = A =
w $ OT L.
J rt k x ion A x I0n 3
I 3 c ^ Amount of Amount of e C
<D -1 cd 0*
No. E Z Reac t i on > *~ Addend -o c s 0
0> 0 0) E CO
react ant addend c Q. k ^ E
M
CO ^ E n n O
O
i **" 2 <D
0> erf _J
CO o
.25 C 2H 6N0 2 + OH~ > CH 3CH:N0 2~ + H 20 A= B = 0.02-0.06 fe AB 25 5.8 0 14.2 1.5 11 * ('H 10 )
. 12 H a
NaCl 0.011 25 5.75 0
0.03-0.05 25 5.55 0
0.06 25 5.75 0
0.09 25 5.85 0
CaCl 2 0.02 25 4.85 0
0.04 25 4.5 0
0.06 25 4. 1 0
-5 (")
.50 CH 3 COCH(CH 3)COCH 3 + H gO > B A - 0.033 Br 2 0.003 kA 21 5.8 CO
25 8.3 -5 cn
CH COC(CH )COCH + H 0+ Go
3 333 -4
35 2.3 18 1.2 9
10 2 A = 4-8 -4 (")
.51 CH 3COCH 2COCF g + H 20 > Et 12* Br 2 0.04-0.08 kA 0 8.99
14 4.65 -3
CH 0 COCHCOCF ~ + H<3 +
3 33 25 1,57 -2 19.7 4 13
M = 0. 1-0.5 25 1.48 -2
Et 16* 25 1.49 -2
Et 33* 25 1.37 -2
Et 50* 25 1.37 -2
Et 67* 25 1.26 -2
Et83* 25 9.27 -3
Et95* 25 6.44 -3
Et6* -3 ( 1 3)
.52 (CH 3) 2CHCH 2 COCH 2COCF3 ^H 20 > A = 0.01 Br 2 0.014 kA 14 3.42
25 1.18 -2 19 1 12
(CH ) CHCH COCHCOCF ~ + H 0 +
322 3 3
CODED SOLVENTS
COMMENTS
General. lonization assumed to be rate controlling step in halogenation and enolization reactions.
For add! tlonal reactions under these categories see 312.47land 112.440. For reverse reactions see 622.450.
Methods: Polarography ( 4)
Hydrogen-deuterium exchange ( ) CO
Substitution (halogenation) ( 7 ) ( 8) ( 10 )( 11 )( 12)
Conduetome trie ( )( ) ( )( )
Thermal Maximum ( )
Steady State, while introducing "B" at controlled rate (9)
Spectrophotometrie ( )
Reactions: (.24)
Valuesof ( 4) include reaction with base of buffer but actual concentration of buffer
not stated. Oo
(-25) Selected dataof ( *) who use reaction rates to calculate dissociation constants
of such bases as CaOH+, BaOH"1' and T10H based on the assumption that OH Is the only base reacting.
(.26)-(.36) Simultaneous reaction with OH~, (.25) corrected for. Integrated form of rate equation
used was: k nK^ + C
(ak
Where. fe g = independently determined rate constant for (.25) = lonization constant of amine,
"a" = initial concentration of A and x = amount of A reacted at time t. (.37)- (.44) Simultaneous
reaction, (.25), with OH~ eliminated by addition of drop of strong acid. Amount shown to be not critical.
LITERATURE
(*) R.P. Bell, M.H. Panckhurst, CSL 1956, 2836. ( 2) E. F. Caldin, G. Long, F. W, Trowse, Co
Nature 1953,171, 1124. ( 3) M. F. Hawthorne, R. D. Strahra, ACS 1957, 79, 3471. ( 4) D.J. G. Ives,
G. C. Wllfcs, CSL 1938, 1455, ( 5) Junell, Arkiv. Kemi. Mineral. Geol. 1934, 11B, 30. ( 6) E.W.
Miller, A. P., Arnold, M.J. Astle, ACS 1948, 70, 3971. (7) R. a Pearson, J.C.P. 1952, 20, 1478.
(8) R.G. Pearson, R.L. Dlllon, ACS 1953, 75, 2439. (9) R. G. Pearson, J.M. Mills, ACS 1950, 72,
CO
1692. ( 10 ) R.G. Pearson, L. H. Plette, ACS 1954, 76, 3087. ( n) R. G. Pearson, F. V. Williams, tn
CD
ACS 1953, 75, 3073. ( 12) R. G. Pearson, F. V. Williams, ACS 1954, 76, 258. ( 13) J. C. Reld,
M. Calvin, ACS 1950, 72, 2948.
k = A =
CO 0) <D
**- L. k x ion V)
0 -o cti (d A x I0n (75
e -H H
So 1 vent Amount of +J ~ 0$ c CZJ
Addend -o c L. S o as
No. React! on 3 " 0 0 (D E u
^Medium) react ant E
o "S c a. 0 -M
.- -H k >40
5 n n O
U- O 1
I
Q
10 2 A= 3; 10 2B=9 -8 * ( i}
, 1 wo,.K ^ aja \'f - Et90* k AB 30 6
59 8 -7
1 C 2H 5~ LC 2H 5H CD
Et60* 60 4 -8 01
(X)
(OH~ CH o -8 t 1)
.2 C gH ONO^ + -j _ >GH 3 GH^O + < + N0 g Et90* 10 2A= 3; 10 2B= 9 k AB 30 3 *
59 2. 1 -6
[G 2H 5 [C 2H 5H
45 4 -8
Et60*
60 2.4 -7
-9 ( l)
(CH 0 ) 0CHON0 0 > (CHJ _C-0 + HNO_ Et90* 1D 2A= 3 *A 75 3 *
.3 <S > a &
- (*)
_ * 10 2 A=3; 10 2B-9 fe AB 59 9 -7 *
.4 Et90*
p H n 80 7.2 -6
(
CH CH^H ^1H2 ^NO -
3 2 |C 2H 5OH 3
fe = A =
of
Amount Demasfineds Temperature fe x K)n A* x 10n
Sol vent Amount of i
act
1onaw Comments 1
tL
ereratu
addend
No. React ion Addend S
(Medium) r eac tant
n n
j'OH"
.5 (CH 3) 2CHON0 2 + J . > Et90* 10 2 A = 3; 10 2 B= 9 k AB 59 9 -7 * (*)
[25 80 5.5 -6
Et60* 60 3 -7
(CHJ C'O + J 2
k 4- NO ~ CO
3 2 C H OH 2
1^ A O
.6 (CHJ CONO o > (CHJ 0C:CH_ + H 4" + NO " Et90* 10 2A = B-5 feA 0 3.3 -7 * (*>
332 32* o
20 5.6 -6
30 2.38 -5 23.5
Et90* 10 2 A = 2-4 NaOH 0.088 feA 0 6 -7
20 1.54 -5
30 5.5 -5 25.4 CO
S ^.UQUJtUOQ
X- * *
C ^
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II S
^ ^
" 5, - J ^H
GO O3
M
a 3 8
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1 1 1 1 1 1 1 i i i i i i i i i i i i i < i i i i
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^ o *^ 1 |
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tO
o o
tO Q
PJ ^ os ^j 8
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8 CV2
0
0 0
T3 K ^ 1 PS
c II 0 0
IO CO IO IO
-o
ac o
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O
0
X
O
CD
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O "^
II
i55 9 ^ 6T w
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t
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i
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c
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CO ^ 0* Q 0 Pd W [x3 O
1 CM
1
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ffi O *^
oIO IO O
O v
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==
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o
^
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0 0^ o o
c S yrl ffi as
o o
t t
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o
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IO
t
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0
'o
0 1 t-p;
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O
t vA^ 0C
' + 4- 4-
g
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o o
3OJ 5 ^
55 55
g 10
g ID
g IO
g O
(T* T* ffi rn
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0 0 0 0
bfl
O
0
m
>- OD a> 2
**
z
Homogeneous Reaction Kinetics
422.451
OT <D k = A =
V) *
si ti V)
So 1 vent Amount of 0 -a 3
k x ion A x I0n D
No. -M g Crf c "S
React i on Addend -o c S <D
<D 0 <D E
(Med i urn) reactant c C
O irt 0. E
E
& ^ O
J * M O OJ
n n O -
1
Q
10 2B=3-21 0. 10 60 9.9 -5
0.23 60 6.3 -5
0.72 60 2.97 -5
OC 60 3.80 -5
CO
. 11 C H CH ON0 0 + p~CH OC H 0~ > 10 2A = 5-6; 9.9-7.4 -4 ( 4)
o o 2
WH M 0.002 k AB 60 *
364
C H GHO 4- p-CH OC H OH 4- NO " B - 0. 10 0.038 60 3.4-3.2 -4
65 364 2
0.062 60 2.35 -4
0.097 60 1.77 -4
0.20 60 1. 11 -4
0.50 60 6.38 -5
00 60 5.63 -5
CO
B = 0. 1 0.063 60 1.22 -6
C H CHO + p-UQ C H OH + NO ~
65 r 2 6 4 2 -6
0.096 60 1.08
0. 19 60 1.00 -6
0.39 60 7.6 -7
00 60 8.5 -7
CO k = , =
o <D
M- L.
CtJ (0 k x in** ,4 x I0n w L.
0 T3 e - ^_, -H
Sol vent Amount of .j C 0) C H
No. React! on Addend l_ B 0 <d
0 0 E L.
QJ
(Medi um) r e act an t 0. E 0)
1 ! fe X n O "^
C 0 E n o
5 0)
Q
1
foH"
20 2.90 -5 * ( 2)
.14 ^sW^.M-^--* Et90* 10 2 A = 3-5; feAB
10 2B =3-10 30 9.85 -5
[25
45 6.15 -4
fH 2
p-CK C H CHO + 4 3 H- NO 60 3.06 -3 22.6 1.9 12
3 6 * C oH OH -6
^ 2 5 SO 8.66 CO
Et60*
30 2.99 -5
45 1.50 -4
60 7.42 -4 21.2 6 10 CO
|OH" ( 8)
km 3D 1.91 -5 *
.15 -CH OC H CH ONO + 4 > Et90* .-,.-.
3642 2 CH CT
L 2 5 r
HO
p-CR OC H CHO + 4 + NO CO
364 OH 2 Oi
LC 2H 5
Qo
km 0 2.44 -1 * ( 2)
+ \ _ > Lt90* ^^, -2
.16 0-NO C H CH ONO 0 5. 18
2642 2 CHO Eteo*
L 2' 5 r
HO
0-NO C H 'JHO + \ + NO
I C 2H 5OH
(OH~
8.74 -4 * (2)
rt-srt^ k AB -10
_ > Kt90*
. 17 rn-NO C H CH ONO +4 0 3.65 -3
2642 2 CHO
I 2 5 f -2
HO 10 1.31
m-NO C H CHO + ^ ^ NO 20 4.56 -2 3D. 6 1.3 14
264 C H OH
0 9.19 -4
Lt 60*
CO
CO * o k = t , ttJ
o at of 3 tt ct 71 CO ^_
Sol vent Amount of T3 E fe X lj[) >i x 10 3
No. 0) c
React i on Addend 1 1 ~o c f > 0)
<D O ID E
(Med i um ; react ant C E
o "2 O.
E * E O +J
4- 0 fe A O
0 03 n n
Q _J
OH"
. 18 10 2 A-3; 10 2B-5 -ID 1 (2)
Et90* k AB 1.01 *
{ W, o 0 3.48 -1
-NO C H CHO + \ 2 + NO ~ JO 1.06 0 17.9 8 13
1C H OH Et 60* 0 7.4 -2
CO
p:
_
. 19 > Et90* 10 2A-3;10 2B-5 kAB 20 8.54 -4 * (8)
C 2H 0 -4
Et 60* 20 2,04
CC)
64
f
-BrC H CHO 4- 1 2
fH 2
n u nu
+ N0 0
*
L<WH
CO
Oi
.20 C 6H B CH 8CH aON0 8 + K Q_ -H, Et90* k AB 60 8.1 -5 * (8) 00
fH 2
C H CH-CH- + < + N0 0
6 ICHOH
V.
foH"
.21 C 6H 5 CH 2CH 2ON0 2 4- J CH Q- > Et90* 10 2A-3;10 2B-5 fe AB 60 3.3 -6 * (8)
L 2 5
C H CHCHO + J 2 + NO"
652 C H OH 2
L * 5
(0 <D k = A =
CO $ L. 0
fe x 10n 4 x I0n (0 k.
e -M H 3
Solvent Amount of ed C
"O C L. g a> a)
No. React i on 03 O E V-
(Medium) re act ant c a. E
E AJ ,4 n O
H- O n 0 .^
C 00
Q
r
feAB 33 1.6 -7 * <>
.22 >CHCH:CH +< 2 + NO ~ Et90*
C H 0~ 6 5 2 ^C H oOH 3
-
{ 25
CO
k AB 30 1.27 -6 * c,
.23 C H (CH )CHONO o + J ^ H (CHJC'-O + J 2 4- NO " Et90*
053 2 CHO" 653 C 0H OH
L 2 5 ^25 (Si
/ 2\
fe AB 10 1.61 -4
(CeH 6) 2CHON0 2 + C 2H 50- -> (C6H 6) 2C: 0 + C 2H 8OH + MO." C 2H 5OH ,0^ S10^ 6 *
.24 -4
20 5.25
3D 1.59 -3 19.5 2 11 CO
Oi
r - fu A ( 8) CD
JOH . JH 20 10 ! A~a 10'B~5 feAB 0 2.98 -5
pc: Et90*
<SO -4
652 2 IGHO"" 662 CHOH 10 1.07
L 2 5 L 2 5 -4
20 3. 17 19.0 5 10
SOLVENTS
Et90* (60) (45) C 2H 5OH V01 % lndlcated + H 2 (l) 2) (4) (5)
Research Council
December, 1958
National Bureau of Standards - National
Homogeneous Reaction Kinetics
422.451
r OMMENTS
General. In aqueous and alcoholic solutions elimination reactions oc.'.r simultaneously with solvolysis reactions which
lead to the formation of corresponding alcohols .and ether. For these reactions see 212.451. Elimination may simultaneously
lead to two types of products, (a) formation of oleflnbyloss of H 7 and NO ~, (b) the formation of aldehyde or ketone by
3
el iminatlon of H"^ and N0 2~. The total reaction involving solvolysis and elimination has been broken up into the individual
reactions by determinations of the amount of olefin, nitrite and the total base consumed.
Reactions. (.!)(.2) Reactions occur simultaneously and are assumed to be of the same order. (.3) Extent of olefin
formation not indicated. (.4) (.5) Reactions occur simultaneously and are assumed to be of the same order. Co
(.6) First order rate law observed and even addition of strong base, OH~, didnotappear to Increase rate more than observed
with salts. Values given by ( 6 ) are for Initial rate since calculated first order constants tended to Increase with the OS
course of reaction in dioxane solutions. (.7) In absence of strong base first order rate law valid. Values listed
by () in dioxane solutions are Initial rates as calculated constants increased slightly with course of reaction.
(.8) Negligible solvolysis observed. (.9) Elimination reaction observed by ( 2) to make up 87% of total reaction.
CO
(.10) (.11) (.12) (.13) Total rate observed is composite of reaction due to C H (f and C H 0". Addition of C H OH shifted 01
65 25 65
Co
the equilibrium from C H 0~ to C H (f and C H OH. Value listed under 00 of C H OH obtained by extrapolation to value of fe
*J O O O A O O O
for LC^H^O j = 0. At high phenol concentrations abnormally large decreases in k were observed which were neglected in
making the extrapolations. (.14) Elimination observed to represent 54$ of total reaction. (.15) Reaction Is
predominantly solvolysis and elimination accounts for only 0.2$ of total reaction. (-16) No observable solvolysis
and elimination accounts for 100$of total reaction. (. 17) (. 18) (.19) Elimination accounts for 96$of total reaction.
(.20) (.21) Reactions occur simultaneously and are assumed to be of the same order. (.22) (.23) Reactions occur
simultaneously and are assumed to be of the same order. (.24) Elimination accounts for only 1% of total reaction.
Co
LITERATURE
(*) J.W. Baker, D. W. Easty, CSL 1952, 1208. ( 2) J.W. Baker, T. G. Heggs, CSL 1955, 616.
( 3) J.W. Baker, A.J. Neale, HAT 1955, 172, 583. ( 4) J.W. Baker, A.J. Neale, CSL 1954, 3225.
( 5) J.W. Baker, A.J. Neale, CSL 1955, 608. (6) G. R. Lucas, L.P. Haramett, ACS 1942, 64, 1928.
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Homogeneous Reaction Kinetics
422.461
k = A
Amount
of Demasfineds actlawion Temper
ature Comments 3
Amount of A x M
No. Addend addend
React ion So 1 vent L.
reac tant
n A n
_J
.7 (CH 3 ) a SC(CH 3 ) 3+ -^CH 2:C(CH 3) 2 H- (CH,) 2 S + H+ Et97* A = 0.02-0.03 = A dL/dt = 50 9.0 6 (7)
r *
=^ (so 1 vo 1 ys i s) feA
.9 (CH 3 ) 2 SC(CH 3) 2 C 2H 5+ > CH 2: C(CH 3 ) C^ + (CH 0) 2 S -- H+ Et97* A = 0.02-0.12 r = A teA 50 9.7 -5 *(*)(*) ( 7 )
Et 80* 50 3.18 -5 t 1)^)
^^ (so 1 vo 1 y s i s)
65 3.05 -4
83 3.29 -3 32. 1 1.7 17
Et 50* 65 1.80 -4
I" = A -3 (3)
. 12 (CH ) SCH CH C H + + C H (T > C <JH O OH A=0.06; B=0. 1 -dB/dt = 30 3.79 *
0.05 0.1 = B k AB 35 1.05 -2
>CH 2:CHC6H 5+ (CH.) 8 S H- C^OH
46 3.98 -2 24 1.0 15
^^ (so 1 vo 1 y s i s)
CO
(0 * o k = <D
L. V)
0 ^
cd cd 3 fe x ion -H
T3 E 3
Amount of C C
<D "0 C <D cd
No. React! on So 1 vent 1 | 0> o L. E V.
T3 c (D E <D
re act ant Q. 0 -M
4- O E fe 71 O ,_
^
<D 0$ _J
Q
= A 5.78 -2 ( 6)
.13 H + (CH ) S + C H 0 OH C 2H 5H A=0.05;B=0.1 r dL/ dt = 64 *
O (6
(CH ) SCH(CH )C H + + C AH D 0~ > CH : CHC DO
o * O O O Na+ = B
fcAB
-^ (so 1 vo 1 y s i s)
- A -dB/dt = -4 ( 3)
.14 (CH 3) 2SCH 2CH2C6H4^-CH 3 + C^CT ^-CH^H^CH^ (CH,) 8 8 + C^OH C 2H 5H A=0.06;B=0. 1 r 30 9. 13 *
Na+ = B k AB CO
-^ (solvolysis)
= A dB/dt = -2 ( 3)
.15 (CH 3) 2SCH 2CH 2 C 6H 4--Cl + C^Cf -^>#-ClC 6H 4CH:CH 2 + (CH,) ,8 + C^OH C 2H 5 H A=0.06;B= 0.1 r 3D 2.18 *
Na+ = B (X)
fcAB
(so 1 vo 1 ysi s)
Na+ = B -5 * ( 4)
(C pj gS+ + OH- __> CHa: CH2 + (c^^ gS + H^ H 20 A = 0.2-0.4; dL/dt = 100 2.4
.16
B = 0.2-0.7 fe AB
^^ (so 1 vol y si s) 100 2.05 -2
Et80* A = B = 0.15 CO
100 2.10 -3 CJi
Et60* A = 0.2; Oo
B = 0.2-0.4
Na+ = B -3 ( 4)
Et 60* A = 0. 1; 100 1.88 *
.17 CH 3 S[CH(CH g ) 2] * + OH" >CH 2: CHCH 3 + CH 3 SCH(CH 3) 2 + H 20
B = 0. 1-0.2 feAB
CODED SOLVENTS
Et97* C H OH + 2.8 wt. % HO (97 vol. % C H OH)
2 O & & Q
December, 1958
National Bureau of Standards - National Research Council
Homogeneous Reaction Kinetics
422.461
COMMENTS
General. Reactants are listed in the order of increasing complexity. First are dimethyl sulfonlum salts In the order of
Increasing numbers of C atoms of the third alkyl group. Straight chain isomers precede the branched-chain isomers. The
dimethyl sulfonlum salts are followed by dlethyl, etc. In almost all cases the elimination is accompanied by a parallel
solvolysis reaction which in some cases may be the predominant reaction. Both reactions appear to be of the same order.
These are listed together with a rate constant k = fe_ + k0 in table 242.461. In this table the derived rate constant for
H, 3
the elimination reaction only is listed. This constant has been calculated from the overall constant by multiplying k by
the fraction of olefln found In the reaction products.
CO
Reaction. (.1) Elimination accounts for 12% and 15.4%of the total reaction at 45 and 64C respectively. (.2) Elim
ination accounts for 7.1% of total reaction. (.3) Elimination accounts for 61 and 65.7% of the total reaction at 45
and 64C respectively. (.4) Elimination accounts for 4.3% of the total reaction. oo
(.5) Elimination accounts for
2.4% of the total reaction. CO
(.6) Elimination accounts for 57.7% of total reaction with 74% of olefin as CH 2: CHC 2H 5
and 26% as CH CH : CHCH . (?) Elimination accounts for 50.5% of the total reaction. (.8) Parallel solvolysls
3 3
reaction negligible and amounts to less than 1% of total reaction. (.9) Elimination accounts for 64.4% and 39.8% of
total reaction In the 97 vol % and 50 vol % ethanol respectively. In 80 vol % ethanol elimination accounts for 47.8%,
49.4% and 53.7% of the total reaction at 50, 65, and 83C respectively. A slight decrease In olefln % with course of
reaction is probably due to a consecutive solvolysls of the olefin. (.10) Elimination accounts for 96-98% of total
reaction. Olefln consists of 86% of CH 2: C(CH 3)C 2H 5 and 14% of CH 3CH-C(CH 3) g. Second order rate law followed for 90% of
reaction course but calculated constants showed slight decrease with Increase in B. (.11) Extent of parallel sol
volysls reaction not stated. At 59C isotope effect S 32/S 34 is + 0.15%. (.12) At 64C elimination accounts for 89.4%
of total reaction. (.13) Elimination accounts for 59.1% of total reaction at 64C. Rate constant extrapolated to
64C from 20 and 45. (.14) (.15) Extent of parallel solvolysis reaction not determined and rate constant given is
for total reaction, elimination and solvolysis. (.16) Elimination accounts for 86%of total reaction in H 20 and 100%
in the ethanol water mixtures. (.17) No appreciable solvolysis reaction in contrast to this reaction in H 20 where
no appreciable olefln formation Is observed and reaction obeys first order kinetics.
LITERATURE
(*) K. A Cooper, M-L. Dhar, E. D. Hughes, C.K. Ingold, B.J. MacNulty, OSL 1948, 3043. ( 2) K. A. Cooper, E. D.
Hughes, C.K. Ingold, Q. A. Maw, B.J. MacNulty, OSL 1948, 3049. ( 3) C.H. DePuy, D.H. Froemsdorr, ACS 1957, 79, 3710.
CO
( 4) J.L. Oleave, E. D. Hughes, C.K. Ingold, CSL 1935, 336. ( e) E. D. Hughes, C.K. Ingold, 0. A. Maw, OSL 1948, 3073. R
( 8) E.D. Hughes, C.K. Ingold, Q. A. Maw, L.I. Woolf, CSL 1948, 3077. (7) E.D. Hughes, C.K. Ingold, L.I. Wbolf, OSL
Qo
-3 -(")
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3 264
-CH tt C H 90 0CH 0GH(CHjOSO
o o 4
10 2B= 6-18
/> rjjj n u QQ rjHlPHCH + i> CH C H SO ~~ + NH
3642 3 " 3643 4
-1 ( 6)
. 14 ^CH 3C 6H 4S0 2CH 2CH(CH 3 )090 2C6H 4^-CH + n-C^NH, -> DW50* not stated feAB 25 1.28
-2 CO
CH 3OH M+N 25 8. 17
+
^>~ CH 3 C6H 4S0 2CH ' CHGH 3 * ^~ GH 3 C6H4 80 3 + n~ C6H l3NH 3 CHG1 3 25 9. 17 -5
25 3.58 -3
CH 3COOG 2H 5
GH 3 C-N - 25 1.36 -2
9
25 3.89 -3 CS)
Dlox*
25 6.08 -4
C 6H 6
0.003 25 2.44 -3
M+N
0.5 25 2.24 -3
CH OH CO
6H 5C1 25 3,08 -4 CJi
OD
-1 ()
.15 DW50* not stated feAB 25 2.35
36422 9 264 3 402
CH 3OH M+N 25 7. 19 -2
^CH 3C6H4 90 2CH:CHCH 3 + p-WJJIJX)- + (n-C^) 2NH 2+ CHC1 3 25 9. 17 -4
CH 3COOC 2H 5 25 3.25 -3
CH aCN 25 3.97 -2
Diox* 25 2.89 -3
C6H 6 25 1.29 -3
M+N 0.0048 25 2.12 -3
0.0070 25 2.19 -3
25 1.26 -3
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tO IO M A3 10 N
< o o 0 CO > CD > CO > 3 r
II II n n n n P C
S S b <
i w m O5 UJk OD kk
a>
g5 3 z M- 1 ,v 3 0
00 CO Ol r^ -h
<* m <
o co Addend
S "
O'
a> 10 Amoun t of
O
K-
E3 M- addend
p. m
0 O ?T Sf <$T Def i ned mass
p EC
<rt to act i on 1 aw
CD O
-1-
8
EC I\D ro ro
Ol Ol Ol Temperatu re
EC
Mo
Ol 00 ^
*
b w o o
ar
X
i i i
CD > 3 ^
.
0 0
w
3 6/
o * H- * Comments
9
O
H H* h*
Li terature
Homogeneous Reaction Kinetics
422.463
COMMENTS,,
General. Reactants are listed in the order of increasing complexity of the alKyl group. Primary precede secondary
precede tertiary except that cycle follow tertiary. Aryl substituted alkyl follow cyclo and sulfonyl substituted alkyl
follow aryl-substituted. Parallel ester exchange to varying extent occurs in acid solvents. See 222.461. Parallel solvolysis
occurs in aqueous and alcoholic solvents. See 212.461.
Reaction. (.1) Rate constant for elimination reaction only, which accounts for about one third of total reaction.
Olefin distribution is 10.3% CH :CHCH 0CH : 89.7% CH.CH'CHCH with 43.2% cis and 46.5% trans-isomer. (.2) Extent of Co
2 & o o o
parallel ester exchange not determined. Rate constant is for total reaction, elimination and solvolysis. (.3) Pro
ducts determined were 50% ester exchange and 31.5% olefin made up of 15.7% CH 2: CHC gH 7 , 35% cis-CH 3CH: CHC 2H g and 49% ^
rorcs-CH 3 CH-CHC 2H 5. (.4) Products determined were 36% ester exchange and 46% olefin made up of 20% (CH 3 ) g CHCH 2CHCH 2 ,
27% cts-(CH ) CHCH : CHCH and 53% irons- (CH ) 2 CHCH-CHCH 3< (.5) Products determined were 12% ester exchange and 68%
olefin made up of 24% (CH g) Q CCR^CH-CR 2 , 1% cis- (CH 3 ) ^CCR- CHCH g and 75% irons- (CH g) gCCH' CHCHg. (.6) Elimination
accounts for only 39% of reaction with ester exchange accounting for 61%, see 222.461. (.7) Elimination accounts
for 85% and ester exchange for only 15% of reaction. (.12) Extent of any parallel solvolysis reaction not indicated. Qo
(.13) (.16) (.17)Rate constant corrected for simultaneous (.12), elimination catalyzed by OH". (.21) (.22) Rate
constant corrected for simultaneous (.30) elimination catalyzed by OH". (.24) (.25) Rate constant corrected for
simultaneous (.23) elimination catalyzed by OH~. (.27) (.28) Rate constant corrected for simultaneous (.26) elimination
catalyzed by OH". (.30) (.31) (.32) Rate constant corrected for simultaneous (.29) elimination catalyzed by OH .
LITERATURE
(*) F. G. Bordwell, R.J. Kern, ACS 1955, 77, 1141. ( 2) F. G. Bordwell, P. S. Landls, ACS 1957, 79, 1593. CO
( 3) F. G. Bordwell, M.L. Peterson, ACS 1955, 77, 1145. ( 4) H. C. Brown, M. Nafcagawa, ACS 1955, 77, 3614. ( 5) C.H.
DePuy, D. H. Froemsdorf, ACS 1957, 79, 3710. ( 6) R. G. Pearson, D. C. Vogelsong, ACS 1958, 80, 1048. ( 7) J. D.
Roberts, W. Bennett, R.E. McMahon, E. W. Holroyd, ACS 1952, 74, 4283. (8) J. D. Roberts, V. C. Chambers, ACS 1951, 73,
5034. ( 9) J. Welnstocfc, R. G. Pearson, F. G. Bordwell, ACS 1954, 76, 4748. ( 10 ) J. Welnstock, R. G. Pearson,
F. G, Bordwell, ACS 1956, 78, 3468. ( u) J. Welnstock, R. G. Pearson, F. G. Bordwell, ACS 1956, 78, 3473.
CD
/s CD ^Q2
x
CD CV2
o in
t3
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to to
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C\J T tO W
w CQ
0
C C t^ CD CO LD ^ COLOLD LO ^J* ^f C!
II Q
*
II III III III 0
M-
O
^_,
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w
C^2 tO
..
00 ^
|
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CD P-.
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i f
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T-l LO Cv TH x1 |jQ
TH 11 II "^ ^ LO
c.
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ii
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O5 i k = A =
C CO o .
M- CO 5 CO L.
H ' TJ 0 -V of 5 3
k x I0n A x I0n 3
c z E -H c -ifJ
Amount of C
<D <ti rt
No. e ,_, Reaction Solvent TJ o c L. 8 E L.
-a <D 0 (D E 0)
Q .
^ in re act ant <c
i!
E
C O.
E
O
O
Q. r~l <C H- 0 /5 n j4 n _J
CO Q
=B -5 (32,
.52 n-C3H? Br 4- C3H 50- > CAOH A = B = 0.1 ^ feAB 55 5.3 *
CH 3CH:CH 2 H- C 2H 8OH + Br"
-6 (30)
.53 (CH J ,CHBr + HO >CH CH:CH + H,0+ + Br" Et60* A=0. 1-0. 15 .. 80 3.2 *
J <c " * O
K+ = B -3 (30,
.54 .10 (CH J 0 CHBr 4- OH" >CH.GH:CH 0 + HO + Br" CA. A=0. 1-0.2; B= 4 feAB 80 1.41 *
3 * 5 2
Na+ -6 (8 1)
.56 (CH o ) * CDBr + C H o0" > V.OT A=0.05;B= 1.0 =B AJAB 25 1.68 *
CH OCD:CH
3 2
H OH 4- Br"
+ c 25
H OD 4 Br~
CD 3 CH:CD 2 + c 25
C4H 8 + C 2H 5H + F~
10 * o
.66 (CH 3 ) 3CF * C 2H 50- > (CH 3 ) a C:CH a + C 2H gOH + T C 2H gOH A=0.8;B= 1 (10.)
KAB 118 1.39 -6 *
en k = A (D
c Def
imas -
ned
ofn
t
Amou Temperature k x v4 x Comments
awon
act
i
1 -H
c o Amount of addend
No. e Reac t i on Sol vent Addend S
0)
react an t -H
Q- O"\
k n A n
dr-t _J
CO
Na+ = B -6 (28)
.67 (CH ) CG1 + C rfH O 0" C 2H 5 H A=0.2;B=0.54 feAB 44 4.3 *
OO
Na+ = B -5 ( 28 )
.68 (CH ) CC1 4 CHS" > C^OH A=0.3;B=0.2 feAB 45 4.83 *
O O DO
0.7 45 4.10 -5
(CH ) c:CH 4- C H SH 4- Cl"
32 65 58 2.02 -4
68 6.02 -4 24.8 4 12
CO
-8 (49)
(CH 3) 3GG1 4 (GH 3 ) 2NGHO B 10 2 A = 6-9 kA 51 9.5 *
.69
80 2.44 -6 25 8 9 1
Na+ -7 (31)
A= 0. 1 ; B= 0 = B kA 25 8.6 *
.70 . 14 ) CBr 4 C 4, H D 0" >
(GH do C 2H 5OH
0.017 0.024 25 1.35 -6
( CH / C CH 4 C H Un 4 op CO
0.064 0.083 25 2.94 -6 Cn
00
0.038 1.0 25 3.00 -5
(2 7)
A - 0.02 (C 2H 5) 4NC1 0.005 feA 25 4.0 -6 *
.71 (CH ) CBr > (CH ) C'-CH 4 H"^ 4 Br~ GH 3N0 2
33 322
0.011 25 4.5 -6
0.020 25 5.3 -6
0.051 25 7.4 -6
0.073 25 8.9 -6
0.098 25 1.10 -5
0.141 25 1.43 -5
k - Q>
Defmaisned-
actlawion Temperature A x Comments
Amount of Addend
No. React! on Sol vent 8
<D
reactant |! A
n n _J
16 40 1.5 -5
0.9 ___ 51 4.3 -5 22. 1 3 10
8.6 (C 2H 5) 4NN0 3 0-.008 51 5.2 -5
8.4 0.042 51 5 rj1 -5
8.3 0.097 51 7.0 -5
8.5 0. 167 51 8.0 -5
8 . Dc \f \~>
n n u ) 4NBr 0.076 51 7.7 -5
.o 0.104 51 8.7 -5 1
.74 \L-n,J
/ PIT \ _L/Dr
p'Rr* ^
-i- Lp n p * nxru pi-i ^
u UUjNnUn ^ v^n p " PU
( PU 0 ^/ rt^-'^n 10 2A =1.4 -6 * (49,
o o 25 3 322 B k A 25 2.3
10-20 39 1.25 -5 CO
8 51 5.0 -5 23 $
0. 10 51 5.4 -5
8 waur 0.09 51 4.9 -5
.75 (CH g ) 3 CBr + C H 5N > (CH ) 2C-CH 2 + C H^H"1" + Br~ -15 -4 (10)
SO 10 2A - &-5; 10 2B=9. 1 -(dA/dt) t=o = k A 1.75 *
17 -15 2.00 -4
41 -15 2.30 -4
NO ~ =B -3 C 1)
,80 (CH ) CCH Br + Ag+ > Et70* A=0. 1;B=0. 14 fe AB 92 1.13 *
3 3 2 -3
109 4.25 22.5 3 10 CO
(CH 3) 2 (C 2H 5)COH, (CH 3 ) 2 C:CHCH 3 , AgBr
A = 0.1-0. 15 fe A 80 3.8 -6 *
t 30)
.82 C3H 7 (CH 3)CHBr + H 20 >C 6H 10 + H^ ^ Br" Et60* CO
K+ = B fe AB 80 1.49 -3 *
( 30)
.83 C 3H 7 (CH 3)CHBr + OH" ^C^o ^ H 2 + Br~ C 8H 8OH A=0.1-0.2;B=4.0
Na+ -6 ( 30)
A=0.2;B= 1.0 = B fe AB 25 2.77 *
.84 C 3H7 (CH 3 )CHBr + C 2H 50- > C 2H BOH
C H rt + C H OH -f- Br"
5 10 25
-6 ( 90 )
Et60* A - 0. 1-0. 15 feA 80 9.0 *
.85 (C 2H 5) 2CHBr H- H 20 ^C 5H io * H^ * Br"
K+ -3 ( 8)
=B feAB 80 2.04 *
.86 (C 2H 5 ) 2CHBr + OH" *CBH 10 + H 2 + Br~ C 2H BOH A=0.1-0.2;B=4.0
Na+ -6 ( 3)
= B fe AB 25 4.00 *
.87 CH OH A= 0.2; B- 1.0
(CJIJaCHBr + C *H o0"
o * 2 5
+ C_H_OH
2 S
+ Br"
10
C 5KH in
-6 * ( l0.j
CHOH A= 1. 15; B= 1.0 feAB ISO 1.21
.88 C H (CH ) CF + C H 0- - 25 -6
25 32 25 140 5.2 23.5 1.4 7
C H + G H KOH - F"
5 10 25
December, 1958
National Bureau of Standards - National Research Council
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Q 1951 No. 0)
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Amount of
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Sr
Def i ned mass-
00 ^ act i on law
J> >^_ ?* Ji> Ji>- [j>
>
rororororo rororo ro w to roro Temp e rat u re
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Comments
O1
'^H' ,_, Ol CJI W ' N . """^L L i teratu re
'
2 ^00 J?
>~'
^
**""'
^
"^
-^ 2'
856 J
Homogeneous Reaction Kinetics
422. 471
i o k = A -
w 0
^r- to $ 1_
0 -u n) n) D
m^ a DJ
A x* in^1 w
T3 -M ^o v^ -LU 3
Amount of C E c
C <ti
<D E ID rt
No. React i on So 1 vent -a c^ -o c E V-
o =J -o <D O <D o
Q.
E
react ant C O
<c i e k n A n O
<t *- O 0) ~J
a> rt h-
0
m+ -6 (64)
.95 C 2H 5OH B = 1.0 = B feAB; 25 k =1.69 *
(CH 8 ) a CHCH a (CH a)CHBr + C^O" >
^ k^s 25 feE=1.42 -6
-^C 6H 12 + C 2H 5 OH 4- Br~ (E) -7
25 k 8=2.7
> (CH a ) 2 CHCH 2 (CH g)CHOH 4- HBr (S)
-6 ( 3) (*)
A = 0.06 kA 25 4.8 *
.96 H ) (CH ) CC1 + H 20 > C 6 H 12 + H 3 0+ 4- Cl~
(n-C 3732 Et80*
CO
K
13
(8)
fe =8.25 -5 *
.97 (n-C3H? ) (GH 3 ) 2 CBr 4- H 20 > BC85* k A; 25
, fe=fe n.+fe t* 25 fe E=2.6 -5
* C6H 12 + H 3 + Br~ < E> 25 fe g=5.6 -5
CS-
J COH + HBr
(n-C JH 7J (CH 32 (3)
*
-6 >(*)( >3)( 67 )
EtBO* A = 0.05 feA 25 6.0 (
.98 (CH 3) 2CH(CH 3 ) 2GG1 4- R 20 >C RH 12 4- H^ 4- d~ -5
36 2.45
45 7.0 -5
55 2. 1 -4 23 5 11
(SS)
fe A 25 4.26 -6 *
.99 (CH 3) 2CD(CH 3) 2CC1 -K H 20 * Et80* A = 0.05
36 1.82 -5
C 6H I2' C 6H n D> H 3^ ra aO+,Cl- .45 5.45 -5
55 1.66 -4
( 7)
k =5.47 -5 *
BC85* feA; 25
. 100 >
<
(CH o ) CH(CH o ) & CBr + HO -5
fe = Vfe
it.
s9 25 k^.Z
~^ C 6H 12 + H 3++ Bl " (E> 25 fes=2.3 -5
* ( CV a^'^a 1 2COH + HBr (3>
*
( 2)( 3 ) (*) ( 4T )
kA 25 1.00 -5
. 101 ^a^s^^001 + H2 -* CeH i2 + H 3^ + Cl " Et80* A = 0.05
-5 * ( 3 )( 4)
.109 (C H ) CC1 + HO > (CH J CICHCH + HO4" -f- Cl~ Et80* A = 0.06 kA 25 1. 10
2 (S 3 2 o 2 3 l
-6 * ( 2)
.110 4- Cl" Et80* feA 0 3.9
3
) CCH (CH ) CC1 + H 2 0 >C 8 H 16 + HO4"
(CH 33232
15 3.4 -5
-4 ( a )( 4 )( 40,
25 LJS5L 22.9 1 13
-5 (7)
BC85* 25 1.19
-3 * ( T )( 8 )
) CCH (CH ) CBr + HO -- Br~ (E) BC85* feA; 25 fe = 1.31
. Ill (GH 33232 2 3
* C 8 H 16 + HO4"
teasteE+fe s 25 -4
*^ (CH 3) 3 CCH 2 (CH 3) 2COH + HBr (S) -4
25 ^=5.6
-5 * ( 9)
WCH i).c( a, i, 1cci + H io-^cA6 >H io^a- Et 80* fe A 25 2.9
.112 O
-5 * () ( 4)
(CH ) 0 CH(C H _> 0 CC1 + HO >c fl H 1B + H 30+ + Cl~ Et 80* A = 0.06 feA 25 1.4
. 113 32252 2 8 16 3
-4 * ( 4) ( 8)
Et80* kA 25 1.05
.114 L \ ^H / .'*' **J ^"l-
OH 3322 o a" i**'A i
-4 * ( 3 ) (*)
Et80* A = 0.06 fe A 25 4.0
.115 (CH 3) 8C(C 2H B) 2CC1 + H 20 C8 H 18 + H 30+ -H a"
(C0-i somer)
-4 * ( a) (*)
Et 80* A = 0.06 fe A 25 1.0
. 116 (CH 3) 3C(C 2H B) aCCl + H 80 -^C9H 18 + H.O* + d'
(/3-isomer)
-6
( 2)
A fe A 25 5 *
. 117 [(CH g) gCCH 2] 2 (CH g)CCl >G 12H 24 + HG1
i 0)
w *
k = A =
CO u
13
Amount of e ~~ ,4 x i n
tti
c
No. 05
React i on So 1 vent T3 C S E u
re act an t c - Q.
e o
E k A o
(D
n n o
J
0) *
Q
.118 [(CH 3 ) 3 GGH 2J 2 (CH 3)CC1 + H gO > C lgH 24 + H^ + Cl~ Et 80* k A 0 2.51 -4 * O
15 1.61 -3
25 5.25 -3 19.6 1.2 IS
Et 90* 0 6.84 -5
15 4.59 -4
25 1.52 -3 3D. 2 1.0 12
CO
Et95* 0 2.62 -5
15 1.95 -4
25 6.65 -4 21.0 1.6 12
. 119 [(CH 3 ) 2CCH 2] 2 (CH 3)GC1 + C gH 5OH >C 12^ 24 + C 2H 5OH 2+ + C1~ C 2H 5H ^e A 15 6.34 -5 * C 8)
25 2.24 -4
CO
35 7.40 -4 21.6 1.5 12
Cyclo-alkyl halides
HO 1 A = 0.5-1 95 1 -7 * (4S)
. ISO cyclo-C H Cl + 2 V > Et 50*
3 o f\ H ru j -5
O K J
-V*. 200 1.3
HO ^
.121 cyclo-C H? C1 + 2 V > Et 50* A - 0.5-1 feA; 95 3.8 -4 *
H 2 1 fe = 1.33 -4 (48>
. 122 c^cio-G HQ C1 -H 2 [ >c>clo-C_H ft + HO + + Cl (E) Et 50* A = 0.5-1 fe A; 95
5 9 C H OH) . 583 -5
95
8 >s^ CH OH, C H n OC H K + HC1 (S)
59 5 8 <c o 95 -5
i fe = 4 =
<t> (D
4- w f. w L.
o -a cti cd n fe x ion 4 x iQn 3
TJ
Amount of C c E C
CD
cti <L> J
No. React i on Sol vent T5
|-S -T3 C E E
-o 3 -a (D O <D E a>
r eac t an t <t o , C a. -H
O
E n n 0
<c 4- 0 CD
cd 1 _l
(D
o
-6 ( 10 tt)
. 123 C>c^C6H liF + C 2H 50- -c,clo-C 8H M + C 2H 5OH + r G 2H 5 H A- 0.9; B= 1. 1 k AB 139 1.76 *
161 8.0 -6
1
(48)
H 2 fe A; 95 9.2 -6 *
. 124 cyclo-C K^ Cl + * Y > Et 50* A = 0.5-1
oil r1 T-f OR fe==/2E+fe s
2 5
-5 ( 33 >
. 125 cyclo-C H Cl 4- OH~ > cyclo-C H W + H 20 -t- Cl~ Et80* 10 2 A = 1.5-3; ^d B/d =k AB 80 3. 11 *
B = 0.11 100 2.22 -4 25.6 2 11 CO
H 00 1 -6 (33) I
Eteo* 10 2A = 2-5 fe A; 80 3.45 *
. 126 cyclo-C H Br + 2 V >
k=k E+k S 100 2.31 -5 25.0 1. 1 10
6 ^ G 2H 5 HJ CS)
Na+ -5 (33)
+ Br~ Et 80* 10 2A = 1.5-3; - B k AB 49.8 8.42
. 127 ^611 J
c-ycio-C H. Br + OH~ > cyclo-C 6 H 11) + HO -3 11
\ 22.0
B - 0. 11 79.8 1.70 22,7 2
(68)
S
6$ 2.3 -6 *
Br *- Cl~ ^ cyclo-C H -*- H + Cl + Br An 90* A = B = 0.07 te AB
. 128 C'vcio-C H
fe A; 25 fe =3.84 -4 (6)
(K) Et 80*
. 129 C H C1+ H 2 0 -* C f> H If + H 0+ . Cl~
cyclo- 1-CH 358
fe ,= 1. 88 -4
fe =/e +fe 25
^^ 1-CH C H OH4-HC1 (S) 25 -4
3 .5 8 *;=i.96
fe =3. 17 -6
( 6)
Et 80* feA; 25
. 130 cycle- 1-CH C H Cl + H.O -^C 7 H i2+ H,0+ + Cr (t, -6
^^^ fe ~fe +fe 25 fe =: 228
^^ l-CH 3 ^H 10 OH-t-HCl (S) 25 V8.9 -7
25 =2.92 -4
( 6)
(h) EtBO* fe A;
. 131 C cio- 1-^H ^ H Cl + H 0 ^ C H -f H 0^ 4- Cl" -4
3 7 12 2 /? = fe -t-fe 25 fe = 1. 38
^^ 1-CH C H OH -f- HC1, (S) 25 fe g= 1. 54 -4
3 7 12
0> k = A = o>
, en
0 TJ w <a ^ k x ion A x ion 3
c -M C
Amount of ~
QJ
No. React ion Addend "^ -S -o c 1! g E
u
=> -a V <r> E *
O
re act ant c '* D. O
CO E E k A O
<D n n _J
t
( l? )
10 2A^1; 10 2B= 3-7 NaN0 3 jj,- 0. 24 k AB 45 1.09 -4 *
. 177 trans-(COO~)CH-C(COO~)Br + OH~ > H 20
0. ID 45 7.8 -5
(bromofumarate) "OQCCJCCOO" + H gO + Br~ -5
0.055 45 6.6
A 5*= -19 (17) (36)
0. 10 70 1.39 -2
(86)
0 70 4.33 -3 17.9 1 9
A j - ( 17) (36)
-2 - id
Et 54.2 wt* 7-16 NaNOg /i=0. 1C) 70 2.04
(36)
70 1. 92 \y
1Q * 7I 7 9
0
K+ =B k AB 50 1.7 -8 *
cis-ClCH'CHCl+OH" >HC:CC1 -*- H 20 + Cl" C 2H 80, i 10 2 A = 2-10;
. 178 75 6.3 -7
10 2B = 2-8
95 6.8 -6 31 1.8 13
i
CO
k = A =
CO X u fe x 10n A x ion v> V-
O T3 3 -H a
C e C -H
Amount of c -M 0) cd O at
No. Solvent *
-o c -a a c
React ion g E
TJ <D 0 o E a>
react ant O <ri c Q- 0
E E fe n A n o
C *- 0 0
<D a) H-
Q
10 2 A= 6;B = 0. 12
Na- =B k AB 30 1^.90 -3 18.7
. 195 ^-ClC6H 4 CH2 C^Br + CJijT C 2H 5H
5 0.10 41 5.85 -3 A/=; -9.2 C 50)
o
H CH:CH AO + CH
-cic 04 OH + Br~ -2
50 1.41 19.3 2 11
Na+ = B -2 (")
. 196 *>-ClC6H 4CH 8CH 8I + C 8H 60- - C2H 6OH 10 A = 6;B = 0.12 fe AB 30 1.05
^50H 10 2 A= 6; B=0. 12
m+ =B fe AB 30 2.03 -2 (M)
.198 m-BrCaH 4CH 2CH 8I +0^0' >
-BrCaH
O 4 o
CH:CH O2 + C.H.OH + i~
Di-aryl-substl tuted aliphatic hallde
10 2 A= 4-8;B= 1-2 Na+ = B fe AB 50 3.29 -6 *
C 11)
. 199 tftreo-CHfC + C 0H.(T
o
> C 2H 5OH
D
3
H )CH(C 6H.)CHC1
o u
75 4.48 -5
tro*^CH.(C + Cl~ K+ -5
A O
HJC:CHC OH O ^ CJJ_OH
O O
O 0.9 = B 75 3. 10
(CH 3 ) 3COH 7
1D 2 A= 5-7;B=0.86 K+ = B -6 * (")
.300 threo-CH^(C H_)CHC1 (CHj ,CO" > ( transJ (CH a)COH fe AB 50 2.93
33
H )CH(C 65
365 -5
0.86 75 4.50
0.60 75 3.76 -5
01
C * <D fe = ^ =
M- 1_ w
o -a SE 5 ^ fe' x 10" 4 x 10n
T3 -H
C
c
S Amount of <D
u-. c -o c cd o LI terature
ReactI on Sol vent ~a C l_ E
No. E <D 0
a = S <c E
rH reactant CL 0
"^ <f .5
7!- o-> E * i_ 0 E jO C3
<c 0) K n A n
O-M 0 J V-
Q
CO
December, 1958
National Bureau of Standards - National Research Council
Homogeneous Reaction Kinetics
422.471 24
O)
c 05i * 0) k = k = o
<4- (n L.
-M 0 T3 S 5 3 k x ion 4 x I0 n 3
c o T3 e - -M
a> z Amount of c c. cd
No. J 0
React i on So 1 vent 0) c| -o c l_ E
1 M -a E o
^ T3 0) 0 <D E
"^ reactant TJ 0 . 0. O
- % <t '^c s E o
CL "-H < C k >i 0 _i
3 <D I n n
CO Q
.219 .34 (-ClC6 H 4 ) 2 CHCHCl2 + OH~ > Et92.6 Wt. * 10 3A=4-10; Na+ =B kAB 20 5.68 -3 ( 12)( 22)
10 2B=2-5 30 1.68 -2 A^ -2.3
(p-ClC H ) ClCHCl + H 0 + Cl~
642 2 -2
40 5.24 20.1 5 12
.221 .26 (C H ) CHCC1 + OH" > Et92.6 wt. * 10 2A=l; Na+ =B kAB 20 3.69 -4 ( 18)( 22)
I
652 3
10 2B=4.7 30 1.27 -3 A$t= -6.5
H ) 0C:CC1 + H 0 + Cl"
(C 652
2 2 -3
40 3.51 20.5 7 11
.222 .27 (-CH o C o H 4 )CHCC1 + OH" > Et92.6 Wt.* 10 2A=1; Na+ =B kAB 20 1.09 -4 ( 12)( 88)
SJ o
10 2B=5.3 30 3.69 -4 A$t=-7.1 se
(-CH C H )C:CC1 + H 0 + Cl"
3642 2 2 -3
40 1.11 21.0 5 11
.223 .29 I>-(CH 3 ) 3 CC 6H 4] 2 CHCC1 3 + OH" > Et92.6 wt.* 10 3A=5; Na+ =B kAB 20 1.07 -4 ( 12)( 22)
10 2B=4.7 30 3.37 -4 20 6 10
|>-(CH ) CC H ] C:CC1 + HO + Cl"
o a o 4 Ss A la
.224 .28 (p-CH OC AHJ 0 CHCC1 0 + OH" > Et92.6 wt.* 10 3A=9; Na+ =B kAB 20 9.18 -5 ( 18)( 88)
O D 4 A O
10 2B=4.7 30 3.03 -4 Ast=--6.1
(^-CH gOC 6H 4) 2 C:CCl2 + H 20 + Cl"
40 9.72 -4 21.4 8 11
.225 .32 10 2A=l; Na+ =B kAB 20 3.03 -3 ( 18)( 22)
(p-FC 6flH 4A ) 0 GHCC! 0 + OH" >
A 3 Et92.6 wt. *
10 2B=4.7 30 9.4 -3 Atft^ : -4.6
(^?-FC H ) C:CC1 4- H 0 -i- Cl"
642 2 2 _p
40 2.67 19.8 1.8 12
.226 .35 (0-ClC6 H 4) aCHCCl 3 + OH~ ^ Et76 wt.* 10 3A=5-10; Na+ =B kAB 20 1.32 -2 ( 18)( 22)
n Q7 n 10 2B=l-5 20 1.89 -2
(^-CIC H ) 0 C:CC1 -H H 0 + Cl" " 92.6 " -2
642 2 2 20.1 2.48 Arf- -5.5
" 92.6 " 30.4 7.11 ~2 18 1 12
en k = A =
c 4- "& * i- k x 10n >4 0 x 10 ^ V) u
o -o oJ ra 3
Amount of -a 6 ^
c c c
c d -t-1 (D cti <D
0) 2: So 1 v en t (D 1- E ?
No. React i on -a 0
E -a e 0
reactant O K$ ex. o
^ L?X "^ E fe A
E ~ tj n n o .t!
(C '
Q. rH <D * 1
CO
10 32 9.22 -4 s
6.7 43 3.16 -3 Als4= -5.6
12 43 2.84 -3 21. 1 1.2 12
.231 H Li >
H CH:CHBr + 2C 65
cis-C 65 (n-C 4H9 ) 20 10 2A=3; feAB 2 3.81 -3 *
(>
10B=1~2
C H C: CL1 + 2C H + LlBr
60 66
Na+ =B feAB 98 2.28 -5 * (as)
.232 trans-C 6 H OR CH:CHBr -f- OH~ > (CH 3 ) 2 CHOH 10B=3.4
98 2.43 -5
13 1.7
C H C.: CH + Br" -f HO
<c 107 6.64 -5
60
107 7.61 -5
S 1.9
118 2.11 -4 A,sf=+4
3.8
118 2.56 -4 31.8 1.3 14
1.9
December, 1958
National Bureau of Standards - National Research Gounci
Homogeneous Reaction Kinetics
422.471 26
05 i
CO 0) fe = A = .
C V.
if. CO ^ TLO y 1 D^ .flA o -* 11U
x n CO
0 -0 3
Amount of -o
" 0 C E " ^ c
<D ^
c
No. Reac t i on Sol vent -o c E u
-a 2(D E (D
-a o
c
"
_!? ITS reac tan t o "S Q- 0
Q. ON E k 4 o
Q. r"1 Jl '~ o O n n -J
J
CO o
-2 ( 23 )
.233 trans-C H CH: CHBr + 2C H Li > (n-C 4H g ) 2 0 10 2A=3J 10 2B-6-12 feAB 2 2.11 *
65 65
H + LlBr
H CiCLl + 2C 66
C 65
Na+ =B -2 ( 2B)
.234 cis-p-UQC H CH:CHBr + OH~ > (CH 3 ) 2 CHOH 10 3A=3; 10 3B=13 feAB 2 6.07
264 -2
7.7 2 6.28 i
C H C:CH + H 2 0 + Br~
-NO 264
7,7 10 1.73 -1 A.Sr^-4.0
7.6 22 5.24 -1 17.1 2 12
( 18 ) CO
Et92.6 wt.* 10 3A=4-10; 11 2.62 -3
10 2B=2-6 20 9.77 -3
25 1.88 -2 AS^+12
-2 CO
30 3.69 23.9 6 15
10 2A=l; 10B=l-2 -4 ( 25 )
.235 trans--NO C H CHrCHBr + OH~ > (CH 3 ) 2 CHOH feAB 43 2.46 *
2 6 * -4
2 50 4.58
1
-NO C H C i CH + H 0 + Br~ -3 A(ST = -10
^264 2 1 61 1.68
1.8 61 1.53 -3 21.3 1.1 10
Na+ =B -5 (18)
Et92.6 wt.* 10 3A=7-8; 10 2B=8.6 30 1.70
35 3.09 -5 Atff=-4
40 5.77 -5 23.8 2 12
Aromatization
Na+ =B -2 A^4== -1.0 ( 18)( 81 )( 67 )
a-C AH A Cl + 30H~ > Et76.1 wt.* 10 4A=4-10; feAB = 1.1 1.9
.236 .38 o 6 6
10 3B=3-10 -dA/dt 20.1 1.70 -1 18.5 1 13 *
(aaeeee configuration) '0 0( 21)
10 4A=4-10; -0.3 2.43 -2
C H Cl + 3H 0 + 3d"" Et92.6 wt.*
633 2 10 3B=3-10 16.2 1.77 -1 18.6 2 13 *
products 1,2,5-17^ -2
Et97.6 wt.* 10 4A=4-10; 7.1 7.7
1 7 2, k-l6%
10 3B=3-10 14.4 1.67 -1 AiS^+6
1, 3, 5-7^0
22.5 4.95 -1 20.0 3 14
05
C <D 0)
i
Def
nedmas - i_ fe A
C Amount of of
Amount 1
i
actawon fe x 10n V Comments
0 addend
0) 2 Addend Ctf
No. E Reaction Sol vent E
<D r-l (D
reactant 0. -H
E fe
Q- r- n _J
3
.236 .38 a-C H Cl + 30H" > (continued} 10A*3; 10B^1 Na+ =B feAB = -2 ( 39 )
Et80* 0 1.50 *
O O D
Et90* -dA/dt -15 2.3 -3
-9 7.05 -3
0 2.00 -2
14 1.09 -1
20 2.28 -1 19.0 3 13
C 2H 5H 0 3.12 -2
r^j
I
CO
.238 .41 fi-C H Cl + 30H~ > Et76.1 Wt.* 10 4A=4-40; Na+ =B feAB = 30.6 2.30 -5 &S$= = +20 t 16)( 21)C") 8
66 6
10 2B=2-9 -dA/dt 50.0 4.71 -4 30.9 4 17 *
(eeeeee configuration)
C H Cl + 3H 0 + 3C1~ Et81.5 wt.* 30-50 30.6 As^ = + 19
633 2
Et89.0 wt. * 30-50 31.4 +22
products 1, 2, 3-^.6%
1, 2, k-Q6% Et 91.2 wt.* 30-50 31.1 +21
1,3,5-9% Et92.6 wt. * 30.6 2.23 -5 Asf=+27
50.0 6.16 -4 33.1 2 J9
Et94.1 wt.* 30-50 32.1 A^+24
Et97.6 wt. * 30.6 1.97 -5 Asf== +22
50.0 4.67 -4 31.7 1 18
Et80* 10 3A^2; 10 2B^1 feAB = 77 2.38 -2 {39)
-dA/dt 90 1.21 -1 32.3 3 18
Et90* 55 1.37 -3
61 3.19 -3
68 8.70 -3
77 3.01 -2
90 1.49 -1 32.3 4 18
k
ementng
i
1
Supp Demafisne-d Teremperatu k x 10n A x 10n
Amount
of actawion
1 Comments
No.
1951 Amount of addend
No. Reac t i on So 1 vent Addend E L i teratu re
r eac tan t
n n
cr> W
i * k = 4 = 0)
0 1-
c M- CO * \_ w
0 -o ctf rt 3
fe x ion A x I0n -H 3
T3 E ~
C C
Amo u n t of C erf
0)
c i
0)
So 1 vent -o c
cd
i_ E
Mo. React i on T! !'
3 -o 0) 0 <t (D
T3 E
reactant o * O
Iv ^in ex
<
'C o E fe ^ 0
< <D n n _J
S: - 0 I
3 Q
0)
10 4A=5-20; Na+ =B
.244 .51 -C H Cl + 30H~ > Et76.1 wt.*
66 6 ( 15 ) ( 21 )
10 3B=5-18 -dA/dt= feAB 10.1 1.42 -2 *
(aeeaee configuration)
20.3 5.65 -2 Ast= +6.5
C H Cl + 3H 0 + 3C1"
633 2 29.7 1.70 -1 21.4 5 14
products 1,2,3-5?? -2
Et92.6 wt. * 10.4 1.47
1,2,4-95*
22.5 8.07 -2 Ast= + 10
1,3,5- 0
-1
30.6 2.03 22.3 2 15
I
Na+ =B (15) (21)
.245 e-C 6 H 6 Cl fi + OH-^C 6 H 5 Cl 5 + H 2 0+Cr See reactlc n (.244) *
Na+ -3 (47)
.246 a,-C QH 6 Cl 4 + 20H" > Et80* 10 8A=l; 10 2B=2 -dA/dt=feAB 29 7. 18 * CO
H Cl + 2H 2 0 + 2C1~
C 642
Na+ ~1 -3 (47)
.247 a-C H Cl + 2C H 0" * Et80* it= feAB 29 *
664 65
(eeaa configuration)
C H Cl + 2C H OH + 2C1~
64 65
47.8t 0-, 50. *<!-, 1.80-
(47)
.248 a -C 6H 8Cl 4 + C 8H 10NH - EtGO* 29 0 *
(eeaa configuration)
Na+ -2 (47)
.249 pr\u ~"^ Et80* 10 2A=l; 10 2B=2 lt=^eAB 29 6.67 *
/-/^ p^n u ^m 4. 4- ^Un ^
(aeea configuration)
C H Cl + 2H 0 + 2C1~
642 2
2. 955 o-, 31. 1^ m- f 66% p-
1 c k = A =
W k. 0
i_
>+- CO * 3 ,4 x ion w
0 TJ cd fe x I0n 3
~o C
e ~~* oj c
Amount of c i_ <L> 0$
-H <D
No. React 5 on Sol vent <D C 13 -D C o E E l_
-o D T? E 0)
reactant Q.
T3 0 J C E O
<C E 0
c *-O k n 4 n _J
<D J
Q
.250 'V
jr \~>
p n rn
u ox ~ pp,T-T~ ^
_L cun *^ v/
P n PI
H ^i. -4-"^ <sn
PP u PPl ~"
n 4-> <ov>->- 10 2A=l;10 2B=2 Na+ ~ d A/ d t = h AB 29 2.72 -1 * (47)
664 642 2 Et80*
(eeea configuration) 28.4^0-, 42. J% m- , 28. 9% p-
Na+
31 I
10 3A=0-1; 10 2 B=1 14 2.78 -2 (39)
.254 'Y-C H Cl ^ 20H~ > C H Cl + 2H 0 + 2C1~ Et80* *
7 655 633 2
Et90* 0 5.92 -3
7 1.58 -2 -
-2 CO
14 4.00
20 7.70 -2 S
28 1.92 -1 20.1 8 13
C 2H 5OH 14 5.18 -2
<SC6H4CH 3-P
CO
Q
00
S0 2 C 6H 4CH 3 -P
S 2 C 6H 4 CH 3
,267 Na feAB 0 2.65
10 3B-2-2.5 12 9.65 16 13
S0 2 C 6 H 4CH 3 -P
,268 10 3A-2-6; =B 0 9.20 -1 (14)
Na
10 3 B=2.5-4 12 3.10 0 15.6 12
COMMENTS
General: Elimination reaction frequently accompanied by for parallel solvolysis reaction. (.62) See 212.471,
parallel solvolysis reaction leading to substitution of hy- .196 for important parallel solvolysis reaction.
droxyl or alkoxyl group for halogen. See 212All. Both (.63)
See 212 All, .197 for parallel solvolysis reaction.
reactions may occur through same intermediate by removal (.64) See 212.471, .198 for parallel solvolysis reaction.
of H by base forming carbanion intermediate with either (.65) Products of reaction not determined. Reaction follow
elimination or substitution of halogen following. For de ed was formation of I". (.66) See 212All, .200 for
tailed discussion of mechanism of elimination and substi parallel solvolysis reaction. (.67) Ratio of elimination
tution reactions see ( 31a). to solvolysis not stated. Total rate measured. (.68) Rate
Classification: The aliphatic halides undergoing elimina constant corrected for thioether formation amounting to 7%
tion are grouped under the headings: Saturated alkyl halide of total reaction. (.69) Products of reaction not deter
(.52)-(.119); Cyclo alkyl halide (.120)-(.140); Hydroxy- mined. (.70) See 212.471, .206 for important parallel
i?
substituted alkyl halide (.141)0142); Di-carboxy substi solvolysis reaction. (.71) Initial rate only as reverse
tuted alkyl halide (.143)-(.145); Halogen substituted alkyl reaction important. In absence of (C H J NC1 no elimination I
halide (.146)-(.151); Substituted cycloalkyl halide (.152)- observed. (.72) Products not identified except for 46%
(.172); Unsaturated alkenyl halide (.173M.187); Aryl-sub- yield of isobutylene. (.73)(.74) Products not determined
CO
stituted alkyl halide (.188)-(.198); Di-aryl substituted alkyl except yield if isobutylene varied between 85 and 100%.
halide (.199)-(.229); Aryl-substituted unsaturated alkenyl (.75) Rate law over course of reaction given by: 85
halide (.230M.235); Aromatization (.236)-(.259); Bridged- -dA/dt = fe AB/(aM + B)
ring systems (.260M.270). where a was found to have an average value of 25. The ini
Reaction: (.52) See 212.471, .183 for important parallel tial rate giving value of rate constant k in absence of
solvolysis reaction. (.53) See 212.471, .184 for im added Br". (.76) See 212.471, .208 for Important paral
portant parallel solvolysis reaction. (.54) See 212.471, lel solvolysis reaction. (.77) See 212All, .210 for im
.185 for parallel solvolysis reaction. (.55) See 212.471, portant parallel solvolysis reaction. (.78) See 212.471,
.186 for parallel solvolysis reaction. (.56) See 212.471, .211 for important parallel solvolysis reaction. (.70)
.187 for parallel solvolysis reaction. (.57) See 212.471, See 212.471, .213 for important parallel solvolysis reaction.
.188 for important parallel solvolysis reaction. (.58) (.80) Relative amount of parallel solvolysis and elimination
See 212.471, .193 for important parallel solvolysis reaction. reactions not determined. (.81) See 212All, .215 for
(.59) Products of reaction not determined. Reaction follow parallel solvolysis reaction. (.82) See 212.471, .216
ed was formation of I". (.60) See 212.471, .194 for for important parallel solvolysis reaction. (.83) See
parallel solvolysis reaction. (.61) See 212.471, .195 212.471, .217 for parallel solvolysis reaction. (.84)
COMMENTS (continued)
See 212.471, .218 for parallel solvolysis reaction. Olefin 58.0% trans] and 3.5% of 2-ethyl-l-butene. (.103) Elim
analysis gave 71 0/cC 2H5CH:CHCH 3 and 29% CH3CH2CH2CH:CH2 . ination reaction yields 21% 4,4-dimethyl-l-pentene, 77%
(.85) See 212.471, .219 for important parallel sofvolysis 2 ra7is-4,4-dimethyl-2-pentene and 2% cis-4,4-dimethyl-2-pen-
reaction. (.86) See 212.471, .220 for parallel solvoly tene. (.104) See 212.471, .242 for important parallel sol
sis reaction. (.87) See 212.471, .221 for parallel sol volysis reaction. (.105) Elimination reaction yields 59%
volysis reaction. (.88) See 212.471, .223 for parallel 2,4-dimethyl-2-pentene and 41 % 2,4-dimethyl-1 -pentene.
solvolysis reaction. (.89) See 212.471, .224 for im (.106) See 212.471, .244 for rate constant for total solvoly
portant parallel solvolysis reaction. Rate constant reported sis and elimination reaction. (,107)(.108) Products of
for ( 7) in 85% n-butyl cellosolve is total rate constant for reaction not determined. Reaction followed was rate of pro I
both the elimination and solvolysis reactions. (.90) See duction of chloride ion. (.109) See 212.471, .244 for
212All, .225 for important parallel solvolysis reaction. rate constant for total solvolysis and elimination reaction. I
(.91) See 212.471, .226 for important parallel solvolysis (.110) See 212.471, .245 for parallel solvolysis reaction. In
reaction. (.92) See 212.471, .227 for important parallel ra-butylcellosolve ( 7) finds rate constant for total solvolysis
solvolysis reaction. (.93) Elimination reaction yields and elimination reaction to be 2.09 x 10~ 5 . In this solvent
80% 2-methyl-2~butene and 20% 2-methyl-l-butene. (.94) S
elimination yields 81% 2,4,4-trimethyl-l-pentene and 19%
See 212.471, .232 for important parallel solvolysis reaction. of 2,4,4-trimethyl-2-pentene. (.111) Elimination reaction
At low [C H5 0~] 81.6% of 2-methyl-l-butene and 18.4% of yields 81% 2,4,4-trimethyl-l-pentene and 19% 2,4,4-trimethyl
2-methyl-2^u5tene produced. At [C H 0"] = 2.0 the % -2-pentene. (.112) See 212.471, .248 for rate constant
2-methyl-l-butene is 71.9% with 28.1 0/? of 2-methyl-2-butene. for total solvolysis and elimination reaction. (.113) See
(.95) Elimination reaction yields 19% (CH ) CHCH CHrCHand 212.471, .250 for rate constant for total solvolysis and
78% transport ) CHCHrCHCH and 3%cis-\CH ) CHCH:CHCH . elimination reaction. (.114) See 212.471, .251 for rate
" 2 _ 3 32 3
(.96) See 212.471, .238 for important parallel solvolysis constant for total solvolysis and elimination reaction.
reaction. (.97) Elimination reaction yields 71% 2-meth- (.115X.116) See 212.471, .253 for rate constants for total
yl-2-pentene and 29% 2-methyl-l-pentene. (.98) See solvolysis and elimination reactions. (.117) First order
212.471, .239 for parallel solvolysis reaction. (.99) rate law assumed from behavior in ethanol-water solvent.
See 212.471, .240 for parallel solvolysis reaction. (.100) Pure chloride decomposes at room temperature. Prepared by
Elimination reaction yields 8*2% 2,3-dimethyl-2-butene and saturating olefin at -40^. (.118)(.119) Only olefins
18% 2,3-dimethyl-l-butene. (.101) See 212.471, .241 produced no solvolysis to give alcohol or ether. (.120)
for important parallel solvolysis reaction. (.102) Elim (.121) Extent of olefin production not stated. (.123) See
ination yields 96.5% of 3-methyl-2-pentene, (38.5% cis, 212.471, .257 for parallel solvolysis reaction. (.124)
COMMENTS (continued}
(.125)(.126)(.127) Extent of elimination and parallel soi- ated rate constant of elimination reaction separately by
volysis not stated. (.128) See 332.771,. 132 for parallel means of the difference in stoichiometry since solvolysis
exchange reaction. (.132) Extent of elimination and consumes two moles of B for each mole A reacting. Rate
parallel solvolysis not stated. (.133) Pseudo first or constants listed are actual rate constants not constant per
der rate lav; followed after rapid reaction of trans-isomer in halogen of ( 38). (.149) Rate constants are extrapolated
mixture, see .134 . Extrapolation to zero time used to deter to zero time since calculated constants decrease with pro
mine relative amounts of isomers present. In mixture starting gress of reaction. (.151) Reaction yields sodium ace
with 63% cis-isomer products were 50% 1,2-dimethylcyclo- tate as final product but acetyl bromide considered to be
hexene and 50% 2-methylene-methylcyclohexane. (.134) product of rate determining step. (.152) Products of
(.135) Pure trans-isomer yields exclusively 1,2-dimethyl- reaction are 84% cyclohexene-ol and 16% of a 1,4 oxide
cyclohexene. (.136) Relative extent of elimination and bridged cyclohexane. (.153) Products of reaction are
solvolysis reactions not stated. (.137) Relative extent less than 30% cyclohexene-ol and more than 70% of the 1,4 i
of elimination and solvolysis reactions not stated. No ap oxide bridged cyclohexane. (.158) Products of reaction
preciable difference in rate for cis-rich or trans-rich isomer not determined. Reaction probably complex involving elim
mixtures. (.138) See 212.471, .264 for parallel solvoly ination and solvolysis. Rate given is for production of HC1.
sis reaction. (.139) See 212.471, .266 for parallel sol Calculated constants drift with course of reaction. Values
8
volysis reaction. (.140) See 212.471, .267 for parallel given should not be considered accurate. (.161) Reac
solvolysis reaction. (.141X.142) Alcohol and ester tion was so slow that alkali in glass was thought to com
yield same product L involving rearrangement. (.143) plicate measurements. Value tabulated is for initial rate.
(.144) Values reported by ( 4R) corrected by ( 46). (.145) (.163)(.165) Rate constant listed only approximate as cal
Reaction followed was rate of formation of Br~. Calculated culated constants drifted seriously. Products of reaction
first or second order constants for rate of disappearance of not determined. (.167) Calculated rate constants drifted
B decrease with progress of reaction. (.146) Elimination except in presence of LiCIO , Products of reaction not
represents only about 9% of total reaction. Remaining 91% determined. (.169) Products of reaction not determined.
is parallel solvolysis. (.147) Rate constant for elimina (.173) Elimination of first Cl~ considered to be rate deter
tion reaction calculated from rate law for parallel reactions mining step followed by rapid elimination of second and
with different stoichiometry as solvolysis reaction consumes third Cl". (.174H.175)(.176)(.177) Dependence upon
second mole of B for production of ethylene oxide. (.148) ionic strength given by:
Rate constants of ( 6) include parallel solvolysis reaction
log k * log k +4 SV/v(l + Aa/"/7) where
in 18.5% yield compared to 79.5% of CHo:CHBr. ( 38) calcul-
S = 1.825 x 10 6(DT)JA = 50.30 x 10 8(DT)" /2 cm- 1 ,a = 5.0^
COMMENTS {continued)
COMMENTS (continued)
sidered to be one of two rate controlling steps for reaction in 2 hrs. (.254) One of the rate controlling steps in
(.240). See also (.254). (.242) Considered to involve the aromatization of y-C H Cl see .240). Rate constant
666
three consecutive steps with rate being controlled by (.243) CO
calculated from composite data for consecutive reactions
and (.255). Rate constant for first step evaluated from initial as well as by direct measurement. (.255) One of the I
rates. Rate constant for second step evaluated from reaction rate controlling steps in the aromatization of S-C 6 H 6 C1 6
of isolated intermediate as well as from composite rate see (.242). Rate constant calculated from composite data l
data, see (.255). (.244) Reaction considered to involve for consecutive reactions as well as bv direct measurement.
three consecutive steps with (.245) as the rate determining (.260) Initial rate, as calculated first order rate constants
CO
step followed by much more rapid elimination of second and decreased with progress of reaction. (.263) Calculated
third HC1. (.245) Considered to be the rate determining second order constants decreased with progress of reaction.
8
step for reaction (.244). (.246)-(.252) Authors show that Behavior consistent with an assumed mixture of 71% trans-
elimination proceeds in four possible ways, trans 1-2, and 29% cis-isomer which reacted 1/85 th as fast, see
trans 1-4, cis 1-2 and cis 1-4 arranged in order of decreas (.262). (.264)(.265)(.266) Calculated first order rate
ing ease. Elimination of second HC1 considered to be rapid constants decreased with progress of reaction. (.269)
with first step being rate determining. Importance of base (.270) Second order rate constants calculated by dividing
illustrated by reactions (.247) and (.248). (.247) Value pseudo first order constants by concentration of B which
only approximate for comparison with rate using stronger was in large excess.
base NaOH see (.246). (.248) No measurable reaction
LITERATURE
C 1 ) M.L. Bender, H. Robbins, ACS 1956, 78, 1699. ( 2 ) H. C. Brown, H.L. Berneis, ACS 1953, 75, 10. ( 3) H. C.
Brown, R. S. Fletcher, ACS 1949, 71, 1845. ( 4) H. C. Brown, R. S. Fletcher, ACS 1950, 72, 1223. ( 5) H. C. Brown,
R. S. Fletcher, ACS 1951, 73, 1317. ( 6 ) H. C. Brown, R. S. Fletcher, R. B. Johannesen, ACS 1951, 73, 212. ( 7) H. C.
Brown, I. Moritani, ACS 1955, 77, 3607. ( 8 ) H. C. Brown, M. Nakagawa, ACS 1955, 77, 3610. ( 9 ) H. C. Brown, Y.
Okamoto, ACS 1955, 77, 3619. ( 10 ) C, A. Bunton, C. H. Greenstreet, E. D. Hughes, C.K. Ingold, 'SL 1951, 647.
( 10ft ) N. B. Chapman, J.L. Levy, CSL 1952, 1673, 1677.
D.J. Cram, F. D. Greene, C. H. Depuy, ACS 1956, 78, 790. ( 12 ) S.J. Crlstol, ACS 1945, 67, 1494. f 13 ) S.J.
Cristol, ACS 1947, 69, 338. ( 14) S.J. Crlstol, R. P. Arganbrlght, ACS 1957, 79, 3441. ( 15) S.J. Cristol, W.
Barasch, ACS 1952, 74, 1658. ( 16 ) S.J. Crlstol, W. Barasch, C. H. Tieman, ACS 1955, 77, 583. ( 17 ) S.J. Cristol,
/ 19> o T
?
A. Begoon, ACS 1952, 74, 5025. ( 18 ) S.J. Crlstol, A. Begoon, W. P. Norris, P. S. Ramey, ACS 1954, 76, 4558. ( ) o.J.
Cristol, D. D. Fix, ACS 1953, 75, 2647. ( 20 ) S.J. Crlstol, N. L. Hause, ACS 1952, 74, 2193.
( 21) S.J. Cristol, N. L. Hause, J. S. Meek, ACS 1951, 73, 674. ( 22 ) S.J. Cristol, N. L. Hause, A.J. Quant, H. W.
( 23 }
Miller, K.R. Ellar, J.S. Meek, ACS 1952, 74, 3333. S.J. Cristol, R. F. Helmreich, ACS 1955, 77, 5034.
( 24 ) S.J. Crlstol, E. F. Hoegger, ACS 1957,79, 3438. ( 25) S.J. Cristol, W.P. Norris, ACS 1954, 76, 3005. S.J.
Crlstol, F. R. Stermitz, P. S. Ramey, ACS 1956, 78, 4939. ( 27 ) P. B. D. de la Mare, E. D. Hughes, C.K. Ingold, Y. Pocker,
CSL 1954, 2930. ( 28 ) P. B. D. de la Mre, C. A. Vernon, CSL 1956, 41. ( 29 ) C. H. DePuy, D. H. Froemsdorf, ACS 1957,
79, 3710. ( 30 ) M.L. Dhar, E. D. Hughes, C.K. Ingold, CSL 1948, 2058.
( 31) M.L. Dhar, E. D. Hughes, C.K. Ingold, CSL 1948, 2065. ( 31a ) M.L. Dhar, E. D. Hughes, C.K. Ingold, A.M.M.
Mandour, G. A. Maw, L.I. Woolf, CSL 1948, 2093. ( 32) M.L. Dhar, E. D. Hughes, C.K. Ingold, S. Masterman, CSL 1948, 2055.
( 33) H.L. Goering, H. H. Espy, ACS 1956, 78, 1454. ( 34) H.L. Goering, D.I. Relyea, K. L. Howe, ACS 1957, 79, 2502.
( 35) J. Gripenberg, K. Sllander, Ada. Chem. Scand. 1954, 8, 383. ( 36) E. Grunwald, S.J. Cristol, ACS 1955, 77,
2891. ( 37 ) H. W. Heine, ACS 1957, 79, 6268. ( 38 ) J. Hlne, P. B. Langford, ACS 1956, 78, 5002. ( 39 ) E. D. Hughes,
C.K. Ingold, R. Pasternak, CSL 1953, 3832. ( 39a) E. D. Hughes, C.K. Ingold, J. B. Rose, CSL 1953, 3839.
( 40 ) E. D. Hughes, C.K. Ingold, V.J. Shiner, CSL 1953, 3827. C 41 ) N. Kornblum, R.K. Blackwood, ACS 1956, 78, 4037.
( 42) Fl. Martin, Z. Bruylants, BOB 1951, 60, 259. ( 43 ) S.I. Miller, R.M. Noyes, ACS 1952, 74, 629. ( 44) T. D.
Nevltt, G. S. Hammond, ACS 1954, 76, 4124. ( 45) A. R. Olson, F. A. Long, ACS 1934, 56, 1294. ( 46) A. R. Olson, F. A.
Long, ACS 1936, 58, 393. ( 47 ) H. D. Orloff, A.J. Kolka, ACS 1954, 76, 5484. ( 48 ) J. D. Roberts, V. C. Chambers,
ACS 1951, 73, 5034. ( 49 ) S. D. Ross, M. M. Labes, ACS 1957, 79, 4155.
LITERATURE (continued)
( 50 ) W.H. Saunders, R. A. Williams, ACS 1957, 79, 3712. ( 51) V.J. Shiner, ACS 1952, 74, 5285. ( 52) V.J.
Shiner, ACS 1953, 75, 2925. ( 53) V.J. Shiner, ACS 1954, 76, 1603. ( 54) V.J. Shiner, M.J. Boslcln, M.L. Smith,
ACS 1955, 77, 5525. ( 55) A.L. Solomon, H. C. Thomas, ACS 1950, 72, 2028. ( 56 ) W. Taylor, CSL 1935, 1514.
( 57 ) T. van der Linden, BDC 1912, 45, 231. ( 58 ) S. Wlnsteln, E. Grunwald, ACS 1948, 70, 828, 841.
k '- A o
ing
Supp
ement
1 Demafisne-d Teremperatu 10n A x 10 n
Amount
of act1awion
Amount of addend Comments
1 -H
No.
1951
No. React i on So 1 vent Addend S L.
react ant -H
k A n
n
K+ -6 ( 10 )
.19 .1 : CH + I ~ + 2Br~
CH BrCH Br + 31" > CH 223 H 0 10 2A=7-14; = B kAB 25 2.63 *
22
B= 1
M99* K"" = B -6 ( 5)
10 2A^2; 30 2.82
10B= 1-2 8.34 -5 ( 5 ) ( ?A )
60
-4 (5 ( 7a )
75 3.72 22.7 7 10
K+ ( 5)
M72* 10 2A~2; = B 60 1.13 -4
10B= 1-2
M63* 30 4.31 -6
E60* ^=0.22 40 2.22 -5
HC1 ya-0.33 40 2.16 -5
KBr yLl=0.44 40 2.01 -5
Na+ ( 4)
C 2H 5H 10 2A = 1.5; = B 25 3.40 -6
B= 0.3 37 1.28 -5
( 10 )
56 9.42 -5 21 8 9
0.05 35 1.65 -3
0.10 35 1,57 -3
0.15 35 1.50 -3
Sup lementing
1 fe A
Demafisne-d fe x >l x ion Comments
1
Amount
of actlawion Temperature terature
Li
No.
1951 Amount of addend
No. React i on So 1 vent Addend S
re act ant
fe n A n
K+ = B -5 *
(M)
.51 4-NaSOC H GHBrCHBrCOONa + 31" > H 20 1Q*A = 2.5;B= 1.0 feAB 25 1.83
364
2.0 n M 25 2.45 -5
1.0 + KBr 1.0 25 2.52 -5
1.0 + KC1 1.0 25 2.58 -5
1.0 -HCaCl^ 0.5 25 2.84 -5
1.0
Na+ = B 25 1.71 -5
2.0 ii n 25 2.24 -5
1.0 + NaBr 1.0 25 2.31 -5
Cyclo-alkyl di-halides
M99* K+ =B -7 *
(")
.52 trans-CH 2CH 2CHBrCHBr + 31" > 10 2 A= 2. 5J B= 0.25 feAB 110 4.5 CO
M99* K+ -7 ( 6)
cis-CH 2 (CH 2) 3 CHClCHCl + 31"" > 10 2 A ~ 3;B=0.26 = B feAB 100 <2 *
.54
M99* K+ = B -7 ( 6)
.55 trans-GH 2 (CH 2) 3CHClCHCl + 31" > 10 2 A ~ 3; B=0.26 feAB 100 <2 *
M99* K+ = B -7 (6)
.56 cis-CH 2 (CH 2) gCHClCHBr -i- 31" > 10 2A = 2,5-3.3; k AB 80 3.80 *
M99* K+ -7 ( 6)
.57 trans-CH 2 (CH 2) 3GHClCHBr + 3I~ > 10 2 A = 2.5-3.3; = B feAB 80 3.05 *
M99* K+ = B 9.51 -7 *
( 6)
.58 cis-6H 2 (CH 2) 3CHBrCHBr + 31" > 10 2A = 2.&-S.3; k AB 80
B = 0.26 100 6.85 -6 25.4 5 9
W
i O fe =
A =
M- W 5 u 0
o -o 3 fe x 10n A x ion
E -M
Amount of C c
No. React ion Sol vent Addend tJ C L. S Q) (0
0) O E
re act ant 1
O (ri c Q- E <u
O -H
E k A
M- O n n O
CD td H- 1
Q
Poly-cyclic dl-bromides
Br~J^l
m\
) ix
+ 31 >
-UJ"
(cho 1 est~2- ene di b romi de)
.
CO
88
A =
A x ID71
Amount of
No. React i on So I vent Addenc
r eactant
CO
&
10 3 A= 5; =B "30 10 1.7 10 D
,67 (CH 3) 2CO Na
21 3.4 1D C
1.2 10 G
91
A =
Amount of
No. Reaction So Ivent
react ant
I
Br j
Br K*
CO
- j kOi dibromochol estane)
x 1 A x I
Amount of
No. Reacti on So I vent
reactant
% reacted time(sees)
(cholest-A--ene di bromide)
JO
8
+ 31"
Br Br
A =
fe x ID" x 10n
Amount of
No. React ion So!vent
reactant
% reacted time(secs)
+ 31
COOCH -30
.73 (CH 3) 2CO = 3; 10-*B= 6.7 =B 1.9 x 10 7
Bn
CQ
JO
Oi
Qo
CODED SOLVENTS
M99* (99.5) (98) (72) (68.3) (63) (60) Methanol wt. % indicated with H SO.
EGO* (68.3) Ethanol wt. % indicated with H o.
Et5* Ethanol 5 volumes + H gO 2 volumes.
COMMENTS
Reaction: (.19) Rate constant calculated by ( 10) based values decrease with progress of reaction. Attributed
on assumed rate law feAB 2 but converted to fcAB which partly to parallel solvolysis reaction. Ratio of rate con
was shown to be rate law by ( 5). (,20)(.21) Rate con stants of solvolysis to elimination reaction is 0.11.
stants converted to seconds irom original minutes ana (.57) Rate constants calculated for first 30% reaction
base e from base 10 logarithms. Second order constants since calculated values decrease with progress of reac
calculated by dividing pseudo first order constants by con tion. Attributed partly to parallel solvolysis reaction.
centration of B. (.22) Values of rate constant extra Ratio of rate constants of solvolysis to elimination reac CO
polated to zero ionic strength. For reverse reaction see tion is 0.22. (.58) Rate constants calculated for first
622.477.85. (.23) No measurable reaction in 22 hours. 30% reaction since calculated values decrease with pro I5T
(.24) By variation of initial concentration ( 7) confirmed gress of reaction. Attributed "partly to parallel solvolysis
reaction order as second order and the stoichiometry in reaction. Ratio of rate constants of solvolysis to elimina
volving 3 molecules of B for 1 of A. Recalculated earlier tion reaction is 0.08. (.59) Rate constants calculated
work of ( 10). Second order rate constants of ( 4) observed for first 30% reaction by ( 6) and up to 20-60% by (^ as
to decrease with course of reaction. (.25) Calculated both found calculated values decreased with progress of s
second order rate constants observed to decrease with reaction. ( ^ found his initial rates to be independent of
course of reaction. (.26)(.27)(.28)(.29) Rate con variation in initial concentrations of both A and B. ( 6)
stants corrected for solvent expansion and empirically de attributed decrease in rate constant to be partially due to
termined salt effect. (.30)(.31) Rate constants of both parallel solvolysis reaction. Ratio of rate constants of
authors corrected for solvent expansion and empirically solvolysis to elimination reaction is 0.006. (.60)
determined salt effect. Reason for difference between A//T = 22.5 of authors converted to E by adding RT.
values not apparent. (.33)(.34)(.50)(.51) Data of ( 10) (.61) Rate constant at 110 not corrected for solvent ex
recalculated to stoichiometry involving 31" and second or pansion. (.64)(.65)(.66)(.67)(.68)(.69)(.70)(.71)(.72)
der rate law by editor. (.52) Rate constant not correct (.73)(.74) Data gives only order of magnitude of reaction
ed for thermal expansion of solvent. (.54)(.55) Rate velocity at room temperature. Probably second order rate
constant limit based upon 1% reaction. (.56) Rate law but accuracy not sufficient to warrant calculation.
constant calculated for first 30% reaction as calculated
LITERATURE
(*) G. H. Alt, D.H. R. Barton, CSL 1954, 4284. ( 2) D. H. R. Barton, W.J. Rosenfelder, CSL 1951, 1048. ( 3) S.J.
g*
Crlstol, J.Q. Weber, M. C. Brlndell, ACS 1956, 78, 598. ( 4) T. L. Davls, R. Heggle, J.O.C. 1937, 2, 470. ( 5) R. T.
Dlllon, ACS 1932, 54, 952. ( 8 ) H. L. Goerlng, H. H. Espy, ACS 1955, 77, 5023. ( 7 ) S.I. Miller, R.M. Noyes, ACS
1952, 74, 3403. ( 7ft ) D. Pressman, W. G. Young, ACS 1944, 66, 705. ( 8 ) L. H. Schwartzman, B. B. Corson, ACS 1956,
78, 322. ( 9 ) A. Slator, CSL 1904, 85, 1697. ( 10 ) C. F. van Duln, R.T.C. 1924, 43, 341. I
t 11 )
J. Welnstock, S.N. Lewis, F. G. Bordwell, ACS 1956, 78, 6072. ( 12) J. Weinstock, R. G. Pearson, F. G. Bord-
well, ACS 1954, 76, 4748. ( 13 ) S. Wlnsteln, ACS 1942, 64, 2792. ( 14) W. G. Young, S.J. Cristol, T. Skel, ACS 1943,
65, 2099. ( 15) W. G. Young, H. K. Hall, S. Wlnstein, ACS 1956, 78, 4338. ( 16 ) W. G. Young, D. Pressman, C.D. Cory-
ell, ACS 1939, 61, 1640.
COMMENTS
Reaction: (.1) Reaction autocatalytlc and could be expressed as the sum of two first order rate constants one uncatalyzed
and the other catalyzed by carbon. In presence of excess carbon simple first order behavior with rate constant k^. Reac
tion rate found to be Independent of surface of vessel. Materials tried were silica, platinum and pyrex. (.3) Reac I
tion shows only slight catalysis by carbon compared to reaction (.1).
i
CO
8
LITERATURE
i
0) 5
k = A
<ri k x lQn A Q x I0n CO
0 -a E """ 3
+J
Amount of d c
L. J
No. React i on So 1 vent Addend c 1 1> 0 0) S E
reactant 3 TJ C """ E 0)
a. O H
i - E k A O
a-. * 03 n n
o
k - A
Demafinsed- fe x ic)n A x ~10n
Amoofunt actlawion Temperature Comments 5
tL
erature
Amount of addend
No. React ion So Ivent Addend E
reactant
n A* n
Defmainsed- fe = A
Amount
of Temperature h xi on A* x Comments Literature
addend actlawion
Amount of
No. React i on So 1 vent Addend B
reac tant
fe A n
n
[. i
Wt. %
.3 C H C:OCH C(CH ) CH COOH > (continued) H 2 H 2 S4 50.7 kA 88 1.20 -4 (4)
25 2322
50.7 100 3.14 -4 ^^=-19.4
50.7 110 6.65 -4 21.6 1.4 9
61.0 79 2.06 -4
61.0 87 3.82 -4 A S*= -20.6
61.0 100 1.05 -3 20.0 5 8
CH g COOH H 2 S4 5.47 81 5.50 -5
5.47 88 7.91 -5
5.47 100 1.29 -4
wt. % M=0. 13 4.92 81 4.96 -5
0. 13 4.92 87 7.33 -5
0.0 4.92 100 9.0 -5
0.13 4.92 100 1.50 -4
0.40 4.92 100 1.59 -4
CO
0.80 4.92 100 1.42 -4 s
. wt. %
.4 n-C gH7 C:OCH2C(CH 3 ) 2 CH 2COOH H 20 H 2 S4 42.8 kA 88 1.33 -5 ( 4)
42.8 100 3.88 -5 + 19.8
C H K CHC:OCH C(CH ) CH C : 0 + H 2 0
2 2322 42.8 109 8.31 -5 22.8 9
50.7 87 3.60 -5
50.7 101 1.10 -4 ^=-20.3
50.7 117 3.70 -4 22.0 8 8
61.0 80 8.34 -5
61.0 87 1.38 -4 Atf* SO. 6
61.0 100 3.90 -4 20.7 5 8
65.4 79 1.35 -4
65.4 86 2.46 -4
65.4 99 6.72 -4 20.9 1.3 9
i fe = A =
! M- CO $ u. jO v jfjl , nn <D
n CO
R> * 1U
jo *v 1U
O -o
Amount of E ~ -H
C c
No. Reaction +-1 03 rt
Sol vent Addend ~ O E
reactant c Q- k A o -H
E n n
H <D O
<D 3* 1-
O
wt. ^
.4 n-C H CtOCH C(CH ) CH COOH > -4 ( 4)
(continued) H 0 H SO 72.5 feA 81 3.50
37 2 322 2 2 4 A 5^
72.5 86 5.60 -4 Aj =-20.5
72.5 99 1.42 -3 19.9 7 8
79.5 64 1.40 -4
79.5 80 5.62 -4
79.5 86 8.64 -4 20.2 1.8 9
wt. %
-5 ( 4)
.5 n-C 4H9 C:OCH 2C(CR 3) 2CH 2COOH > H 2 H* 80* 50.7 feA 86 4.43
50.7 100 1.27 -4 + -21.5
n-C H CHCrOCH C(CH ) CH C:0 + H 0
37 2322 2 109 -4
50.7 2.65 21.4 5 8 I
65.4 80 1.81 -4
65.4 87 3.08 -4 A^-21.7
65.4 100 8.09 -4 19.8 4 8
72.1 80 3.82 -4
JO
72.1 86 6.77 -4 A^=-20.9
72.1 97 1.43 -3 19.8 8 8
s
wt. %
-5 ( 4)
.6 (CH ) CHCH C:OCH C(CH ) CH COOH > H 0 H SO 61.0 feA 100 2.7
32 2 2 322
61.0 110 5.05 -5 A a T-=-35
(CH ) CHfcHC:OCH 2C(CH g ) 2CH 2t:0 + H 20
61,0 117 7.5 -5 17.3 4 5
.7 CH CH COOC H -5 ()
CH CHCOOC H C 3H 8OH A = 0.10 C H ONa 2.85 feA 35 2.8 *
, 2 2 2 5__^ / 2 ^ 2 * + C H OH 2 5
0.11 2.85 40 5.3 -5
CH CH COOC H CH CH C:0 2 5
22 25 22 -5
0.20 2.85 40 5.7
0.1 2.85 45 1.07 -4
0.1 2.85 50 2.6 -4 24 5 13
w
i k = ^ =
05
M- A x I0n
O TJ 3
k x 10 3
Amount of C E c
-H (D -D c CD
No. React ion Solvent Addend 0 0 E E 2
<D E (D
reactant 0 (ti Q. ^ 0
e e k n n 0
'C
V-
Q
A=- 0.1 -5 ( 3)
.9 CH 2 CH rt COOC 0H e ^ 0H K C H OH C 2H5 ONa 2.85 feA 35 2.68 *
^ , + C ^ QH
/
CH fl CHCOOC
_^ -5
40 3.93
CH 2 3 -5 9
2 3 25 45 6.38 17 1
-5 ( 3)
.10 CH CH COOC H CH CHCOOC^H CH OH A ~ 0 .i CHONa 2.85 feA 35 2.20 *
2 25 __^ / 2 \^^ 25 + QH 2 5 2 5
40 4.20 -5
1 2
CH CH(C H )COOC H CH CH (C H TC : 0 * 5 -5
225 25 ^25 45 7.92
50 1.17 -4 25 3 14
.
JO
-5 ( 3) S^
GO
.11 3H COOC H CH CHCOOC H C H OH A^-0.1 C HONa 2.85 feA 45 2.10 *
?2 '"^ / ""^^^x^ + p u nu 2 5 2 5
CH(i-C 3H 7 )COOC 2H 5 CH 8CH(i-C^CsO 2 5
CODED SOLVENTS
COMMENTS
Reaction. (.1) In non-aqueous solvents Is second order with respect to A. In aqueous solvent reaction is first order
with respect to A and reverse reaction is Important, see 632.441. In mixed solvent 90% (CH ) CO and E^O combined first
and second order equation followed. Authors observe that in non-aqueous solutions the second order rate constant varies
inversely with the square of the concentration of the oxygen containing solvent component. (.2) Selected data. Plot
of log fe vs. log [H SO ] is linear with slope of 4.6. Rate constants do not correlate with H function. (.7)-(.11)
Rate constants calculated from combined rate constants k + k for forward and reverse reaction and equilibrium constants.
Units converted to seconds from original minutes.
I
C-4-
8
LITERATURE
f 1) T. Henshall, W. E. Silbermann, J. B. Webster, ACS 1955, 77, 6656. ( 2) J. Koskifcallls, Acta. Chen. Scand. 1956,
10, 882. ( 3) R.I. Reed, M. B. Thornley, CSL 1954, 2148. ( 4) W. E. Sllberman, T. Henshall, ACS 1957, 79, 4107.
i (D
H- L.
fe =
o -o in
3 k ^ 10 n D
o " e ~ -H
c -M
C
Cti (D
"c **"* i-
No. So 1 vent Addend' I 5 <D O
G
React! on 3 O 0) E <D
o 1 C '^ D. k 0
E ^ 0 E n O
<ci h-
Q
-4 (V 2)
.1 C 6H 8N=C(CH 3)CH 2C:OCH 3 - f I JH " + V H 2 +H 2 S4 97 ' 3* A=0.1 feA 25 3.50 *
^xV/'^^V Ss 95.7 25 2.05 -4
93.3 25 1.03 -4
?
CH -5
3 91.2 25 5.70
89.2 25 3.52 -5
88.6 25 2.75 -5
-4 *
( 2)
.2 2,4, 6-D gC H 2N=C(CH 3 )CH sC:OCH 3 > 1
/W JJ 1 + HOD H 0 + H SO 95.7% A=0.1 feA 25 1.35
2 24
89.2 25 2.68 -5
N 3
-3 f 1)
.3 4-CH C H N^C(CH ) CH C;OCH 3 > f |j | HS + H 0 H 0 4- H SO 95. 5 A-0.1 feA 25 1.41 *
2 2 4 93.1 25 7.15 -4
91.1 25 3.53 -4
CH 3 v' V 89.2 25 2.05 -4
CH 87.6 25 1.23 -4
3 -5
86.3 25 6.45
84.5 25 3.98 -5
H 0+ [H SO 1=14. 42 NH 4HS0 4 2.0 25 2.18 -3
2 2 * 10.14 4.0 25 9.23 -4
7.97 5.0 25 5.23 -4
5.80 6.0 25 2.87 -4
1.36 8.0 25 4.97 -5
COMMENTS
Reaction: (.1) Selected data, units converted to seconds from original minutes. Plot of log of rate constant vs. H is
linear. (.2) Units converted to seconds from original minutes. (.3) selected data, units converted to seconds
from original minutes. Plot of log of rate constant vs. H Q is linear for H 0-H 2 SO medium and plot of log of rate constant
vs. log ([H 2 SoJ/[HS0 4~]) Is linear In both media.
i
-
CO
&
LITERATURE
T. G. Bonner, M. P. Thorne, J.M. Wllkins, CSL 1955, 2351. ( 2) T. G. Bonner, J.M. Wilklns, CSL 1955, 2358.
fefe xiO n
A =
w Ax 10 n
c Amount of action
ima IONA
ned
Def Temperatu
0) E
No. Reaction ~o ^
reactant
,o n ,o n
10 4A = 5-14 kA 30 2.68 -7
.3 NO N-C(NH )NHCH CH(CH )ONO > NO NCH(CH ) CH HN'CNH + + NO 3
2 32 2
2 2232 -6
40
50 4.99 -6 29 1.3 14 +4
COMMENTS
Reactions followed by conduc time trie method as well as analytically for M. Conduc time trie method indicated slightly
higher extent of reaction after about 75%. This was attributed to hydrolysis of product and rate constants were corrected
for it.
LITERATURE
C. Boyars, W. F. Sager, S. Skolnik, ACS 1957, 78, 4590.
k =
k x 10 n A x io71
No. Amount of
React I on So I vent
reactant
CODED SOLVENTS
An50*(5) (CH ) C'O % Indicated and H 0 (wt. or vol. % not Indicated)
COMMENTS
Reaction: (.1) (.2) (.3) Reverse reaction negligible. Units converted to seconds from original minutes. (.4) Value
of rate constant derived from first stage hydrolytic reaction, 212.471(.421), of "mustard", s(CH CH Cl) with added ttilo-
phosphate. Units converted to seconds from original minutes.
LITERATURE
(*) P. D. Bartlett, C. G. Swain, ACS 1949, 71, 1406. ( 2) G.M. Bennett, F. Heathcoat, A.N. Mosses, CSL 1929, 2567.
fe = A =
0)
M- W * k x 10n ,4 x ion
0 -o 3
Amount of -H
C E
"c ^ <d
React f on So 1 vent -D -o c E
No. tJ
<D
reactant c
E d E k n ^ n
"C (U
0) * h-
Q
.1 C 6H 5N(CH 3 )/ + CH 30- -> C 6H 5N(CH 3 ) 2 + (CH,) ,0 CH g OH 10 8A'v 2;10 2B-4 r = A feAB 69.8 9.71 -5
Na"1" B 80.9 -4
4.39
95.3 2.69 -3 32.7 7 16
.2 ^CH 3 C eH 4N(CH 3 )/ + CH 30- - ^H^NfCH,) , + (CH,) ^ CH o0 OH 10 2A-2;10 2B-4 r = A feAB 69.7 5.66 -5
Na = B 80.9 2.67 -4
95.2 1.68 -3 33.3 1.0 17
.4 m-FC H N(CH ) + + CH 0" > m-FC H N(CH ) + (CH ) 0 10 2A-2;10 2B-4 r = A feAB 58.3 7.80 -5
64 3232
64 33 3
CH 0o OH
Na+ = B
69.2 3.59 -4
2 4 80.9 1.71 -3
4 2 80.9 1.71 -3
4.1 4.1 80.9 1.38 -3
3.7 8.0 80.9 1.25 -3
~2 ~4 91.4 6.22 -3 31.8 7 16
.5 -FC 6H 4N(CH 3 ) 3+ 4- CH S0- > ^-PC^CH,) 2 + (Cig ,0 10 2 A-2;10 2B-4 r+ = A ftAB 58.6 3.44 -5
CH o0 OH ~ t>D 68.9 1.52 -4
80.7 7.50 -4
91.9 3.13 -3 32.6 9 16
LITERATURE
W. L. Bevan, G. C. Bye, CSL 1957, 3194.
<u fe =
10n
Amount of Defined mass Temperatur Cotsmmen
No. R eact i on So 1 ven t
reactant act i on I aw
teo
n
. 1 2 (CH 3) 2 CN0 2- 4 2H+ ^>2 (CH,) 2C:0 4 N 20 4 H^ 80 vol % CH OH 4 H 0 10 4 A'^7; 10 2B- 2-10 0 1.30 -2
o 2
.2 2 CH 2 CH 2CH 2CN0 2"" 4 ai* >2 CH 2CH 2CH 2 C-0 4 NgO + HO 80 VOl % CH_OH 4 H.O -cIA/d= k AB 0 -1 *
O A
1 f ^ r- _,., ......j
.3 2 CH 2 (CH 2) 3 CN0 2 + 2H >2 CH 2 (CH g} 3 G-0 4 N gO 4- HgO 80 vol % CH 00OH 4 H A00 10 4 A^BjlO 2 B = 4 20 -dA/dt= k AB 0 5.3 -3
.4 2 CH 2CH 2CH(CH 3) GN0 2~ 4- 2H* >2 CH aCH gGH (CH g) ClO 4 NgO 4- HgO 80 vol % CH oOH 4 H 00 10 4 A^6; 10 B = 1-5 --dA/dt= ^ AB 0 4.5 -3
.6 2 &i 2 (GH 2) 5^ 2 ^ ^ > 2 ^2(^2) 5^0 + N 20 4- H 20 80 vol % CH OH 4 HO 10 4 A^5; 10 2B= 5-20 dA/dt = & AB 0 2.3 -3
0 <t
COMMENTS
i General. Ac! formof nitro alkane produced by addition of alkali prior to reaction. Pseudo first order
rate constants converted to second order constants by dividing by concentration of excess acid added
OFFI:PNT
RINTCINEG
at start of reaction.