Professional Documents
Culture Documents
1965
Recommended Citation
Chen, Der-Rong, "The kinetics and mechanisms of the reaction of benzyl chloride with potassium t̲-butoxide in t̲-butyl alcohol"
(1965). Masters Theses. 6957.
http://scholarsmine.mst.edu/masters_theses/6957
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THE KINETICS AND AffiCHANISMS OF THE REACTION
BY
THESIS
Rolla, Missouri
1965
Approved by
TABLE OF CONTENTS
Page
LIST OF FIGURES ••••••••••••••••••••••••••••••••••••• iii
LIST OF TABLES . ... ..... ...... .... .. ...... . . .. ....... ··iv
ACKNOViLEDG.EMENT ••••••••••••••••••••••••••••••••••••• v
I. INTRODUCTION ..................................... . 1
II. REVIEW OF LITERATURE .. . ... .... . . .. ..... . . ....... 2
III. EXPERIMENTAL
t-Butyl .Alcohol • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 13
MECHAN'ISn.iS • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 35
BIBLIOGRAP.Irr • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • .. • . • • • 39
APPENDIX (Least Squares Computer Program) • • • • • • • • • • • 41
VITA • • • • • • • • • . • • . • • • • • • • • • • • . • • • • • • • • • • . • • • • • • • • • • • • 51
iii
LIST OF :FIGURES
Figure Page
1 Short-path Fractional Distillation .............. 15
2 Distillation o£ t-Butyl Alcohol ••••••••••••••••• 16
3 Electrometric Method £or the Determination
of Chloride Ions ••••..••.•.••.••••••.•••••.••... 22
4 Plot of Second-order Rate Constants on
a log Scale vs. 1/T £or Determination
of Arrhenius Activation Energy, Ea •••••••••••••• 32
iv
LIST OF TABLES
Table P~e
ACKNOWLEDGEMEN!
I. INTRODUCTION
--ora
R CH2-X
slow
fast
Ro;lf:! + x-
Sw1
Rvlf:! + HO-
fast
R-oCH20H
(The ionization of (X) is retarded by electron-attracting
groups.)
----R o~OH + x-
(1) s. C. J. Olivier, Rec. trav. chim., ~' 687 & 996 (1930).
(2) M. Simonetta & G. Favini, J. Chem. Soc., 1840-4 (1954).
3
ArCH 2 Cl ArCHCl
lA.rCH2Cl
-RCl
ArQH:::;:;CHAr ArCHCH Ar
l . 2
Cl ·:·
Similarly ~or the ~ormation o~ ~,~'-dinitrostilbene oxide
~rom ~-nitrobenzaldehyde and ~-nitrobenzyl chloride in the
presence of base either a methylene mechanism or a conden-
sation-dehydrohalogenation mechanism may be written.
ArCHOl !!reHO
ArCII- CHAr ArCH-CHAr
I I "'-I
c1 o- 0
chloride.
Although the report by Hanna, Iskander, and Hiad is
in agreement with the hypothesis that a methylene inter-
mediate is formed in the reaction, it gives no direct
evidence concerning the mechanism by which the methylene
is transformed to ~,~'-dinitrostilbene. This point will be
discussed in relation to a closely related study of the
re~ction of ~-nitrobenzyldimethylsulfonium ions with sodium
hydroxide that was carried out by Swain and ~hornton.
7
CH CH CH CH CH CH
3 3 3 3 3 3
"';/ ~/ ~v
I - C-H
f
11
C-H '
I
-H
.
0 N0
2
.. Jo
0 N0
2
.,..
N0 -
2
.. )lr etc •
Ar-C-H
Ar-C -K ----~·:ArCH=CHAr
1Ar0H~e 2 -Me S
2
Ar-CH-CI1-Ar
I
+SMe 2
phosphine.
III. EXPERIMENTAL
A. PREPARATION OF MATERIALS
- Disti~late
.1
Distillation flask
. ®,---..~.. :
KINETIC DATA
Run 2!.
The temperature is 30.0°0.
Concentration of benzyl chloride = 0.03086 mole/liter
Run 2B
The temperature is 30.0 0 C.
Concentration of benzyl chloride = 0.03349 mole/liter
Concentration of potassium t-butoxide = 0.28982 mble/liter
Time in hours 15.00 26.00 43.00 61.40
ml. of Agl!f0 4.60 6.60 10.60 13.70
3
Average value of k = 1.0923 X 10- 5 liter/mole-sec
Run 2C
The temperature is 30.0 0 C.
Concentration of benzyl chloride = 0.03002 mole/liter
Concentration of potassium t-butoxide = 0.29892 mole/liter
Time in hours 11.80 22.70 34.30 53.80 77.20 102.80
ml. of AgN0 2.66 5.10 7.10 10.30 13.10 16.20 *
3
Average value of k = 0.96045 X 10-5 liter/mole-sec
Run 3A
The temperature is 30.0 0 C.
Concentration of benzyl chloride = 0.03084 mole/liter
Concentration of potassium t-butoxide = 0.59784 mole/liter
Time in hours 18.75 47.50 66.70 83.80
ml. of AgN0 7.08 14.50 16.90 19.30
3
Average value of k = 0.81646 X 10-5 liter/mole-sec
Run 3B
Run 3C
The temperature is 30.0 0 C.
Concentration of benzyl chloride = 0.03280 mole/liter
Run 4A
Run 4B
The temperature is 30.0 0 c.
Concentration of benzyl chloride = 0.06061 mole/liter
Concentration of potassium t-butoxide = 0.59568 mole/liter
Time in hours 13.40 23.50 41.50 60.00
ml. of AgN0 10.90 18.20 26.10 32.90
3
Average value of k = O.tJ7934 X 10- 5 liter/mole-sec
Run 4C
The temperature is 30.0 0 c.
Concentration of benzyl chloride = 0.06001 mole/liter
Run 2D
Run 2E
Run 3D
Run 3E
Run 4D
Run 4E
Run 8A
Run 8B
Run 6A
Run 6B
Run 6C
Run 7A
The temperature is 59.7 0 C.
Concentration of benzyl chloride = 0.10040 mole/liter
Concentration of potassium t-butoxide = 0.09880 mole/liter
Time in hours 4.60 7.50 15.00 22.00 27.40 31.40 43.00
ml. of AgN0
3 18.60 26.50 37.50* 47.70* 52.50 54.30 59.00
Average value of k = 18.340 x 10-5 liter/mole-sec
30
Run 7B
Run 9A
Run 9B
Avg. k, .L.(mol-sec t 0 c• T, 0
.K. 1/T x 10 4
40 j
30 -
20
10
9
8
lt')
....
0
7
~
C'l 6
,.!ol
3 -
30 33
3 3
IV. DISCUSSION
ln A/(A-X) = kt
1 B(A-X)
k2 = - - - ln
A-B A(B-X)
Where A = initial concentration of benzyl chloride
B =initial concentration of potassium t-butoxide,
X = amount reacting in time t
T.A13LE II
Second Order Rate Constants for Reaction of
Benzyl Chloride with Podassium t-Butoxide in
t-Butyl Alcohol at 30.0 C.
Run No. Cone. of Halide Cone. of t-Butoxide k 2 x 10 5 M- 1 sec·
average 1.01240
average 0.84301
average 0.92642
35
MECHANISMS
slow, rate-determin-
ing step
Qcn: + Qcn:
' or] fast
QcH 2x + :B
Qcnx~Q +E
36
(C)
slow, rate-deter-
0 CH 2Cl.+ 1-BuO-
mining step, k 1
fast, k_ 1
> 0 CRCl.,- + ,1-BuOH
+ _1-BuO- .fast, k3
------+- 0 CH=CR 0.
+ ,1-Bu.OH
37
(A)'
But
There.fore,
(c)•
d (c 6R5ca2 cl) =
dt
BIBLI OGRAJ?HY
APPENDIX
n n 6 I''= 1. , ;.j
''I; 1\0 1 0:' 1 T F.i;P
PII I 1CH 20n ,T Ei ;p
" r: f I) l () 6 ' L
" ( I () !: =l ' L
nr- i·.n 11)6 , ;, )
l
:: 1' =1'
., r: t\ 11 1< 1n , c x1i L c1 l , I - 1 , r ~ J
1: F f\1 l 1 (H) , ( II ( I ) , I = l 1 ; I )
! ~ •: /\ " 11 C) , f\ , i ~ 1 I~ 1 S , C .~
J.!i 7 1 1\ 1 p,
i> I I; 1C~ I
f'' l ?. !=1.,' '
T { T ) = ::;t, 'H' • :.!: 1 I { I )
:: ( 1 ) =;:;, L (I ) ~~tl~ / 5 .
7. Y CI l=LI H;i"= C H~::C/1. - {:::X (I) )/( A>::( f-3- S>::X ( I)) ))/ ( A- ' : )
C u:i\ ST - S fll! Af~E S f=ITTI Hf, Of Dt\TA
S I I! : ;~ - U • Cl
~ll i\ Y=O . t:1
~'I I: j ;: '( =() •I)
S I I; j ~: / : () • ()
11 r • :~ I = 1 1 fl
~ I' . i ;: =T ( I ) +SU I: ;~
S II i l Y = Y ( I ) + S I I i ;y
S llj i XY = T ( I ) :.:: Y ( I l + S l.ll i XY
3 !'II : .;~~L=T ( I ):.:::;:?.+Sil r~ X2
11 r j: =;::: ::: St ,. i ;: ?. - s l! i ;;: :;:::: 2
SLilP •.-: = ( ~~:, :::S l li ·l::Y -SII i iX:::SII IW ) / Dt:: t
r: :.rIS T = ( Sll!l X z:::su ! iY- S Uli X::: SU I·lXY ) /OE/-1
Pl !i !C I ! l !.l l 1 S LOPI: 1 Cll i'I ST
C CA LC ULA TE OF I~ OIVIOUA L SLOPES
f)l}L;. I=l, ll
C:\LC I(- Y<I) IT C I)
!'I r: L (I > = S U l PE - C/.\ LCl(
' :· D l'l I II c 1 0 2 ' T ( I ) ' J\ L c c :< ' 0 E L { I )
C sT:-\T IS t! c:\1. TR £:J\ TI 1 E 1 ~ l f);- I HE UAl/\
nrLl=O . Ow
nr-L2=0 .0
- '
ns L OP=f\~SF ( OEL (I))
11 '-: Ll= US LDP+Or:L l
!1· 1>1: L ?.=l 1SLOP :~ ~';:f+D 1: Ll
APF.V=I JF. L J./Xtl
42
r ::l ·.c.:: ~: T lJI.:\111\ TIO ; ~ :\T 9 5 C Oi ~ Fii>::• ' Cc Ll: " :: L == ·~:-C . ':· C"'~
C:'~i:C nF RCL = . 061':·6 CIJi' tC r1;: u ' tr1 - == • <.~ 56f~
fA SU•Pr: ,; U. 10600E - v':·liTtR/: i nL:: - s :;c r: 'i . ·u -..·T = 0 . 64217': - 0 l
'!' !! ::= 6L,G00 . 00() E:: :; CDi'ST -0 . 1161()1: - tV:- ) !::'· =- 0 .101 66E - 05
T r :: F.=1 27 0 UO. nno E}:P cn:·1ST = O . 11072":- 0t:. ·)!:' = - 0 . t;- 7 ?.59E - 06
T!• . !==J. 6 aL:. f; () . 0'!0 EX~) COi : ST = O . l09<.J~>r:: - n .~·. '•~· =- 0 . 3959RE - 06
.t\ 1'1:!).:\GE DEVI/'.t I OH = 0 . 62n':·OE - Of)
S T t\ i •n /·.P.n !J EV I,').. T I 01 = 0 . 4r. 5'~0 =- :16
P 1 : f~CE i 1 T DE'.' ! i\ Tin f·t hT 9 5 CGi! FI DE:lC..: L ~' ' ~: L = ~ . 159
::r)' C flF ~CL - • 06061 COi·!C £lr 1., 1.1 : = 9? 68
4/J SLDPr: = 0 . {; 7 9 3'~E -05LI T E1.'!;iOLE - S EC (. l j• ~ Tt. i IT ; 0 . l 3 8 53 E - 0 1
TI:: r:= ':- 02t;O . OOO EXP COf·JS T= O . f-1 7 87?.: - o~ ) •:· = 0 . 61J.7 2E-OO
=
T r: ;F. c '~ c, oo • oo o Ex P ca>!s T-o • 9 3 un r: - o :') )!: .. =- 0 • 5 2 L~ 7 6 E - 0 6
T r r:F.= lt~9L~OO . 000 f: XP COilS T=O. 8 721 3~ - 0 5 l F" = 0 .72 0H5E - 07
Tr :: r:=?. 16000 . 00 0 EXP COI•!ST =0. 08 95 M :-()5 ' F. ' ' =- O . J. O~Z?.E - 06
AVEnAG E DEV I AT ION = O . l763 0E - 06
S T 1\1 1n 1\ R D D EV I AT I 0 ~; = 0 • 15 5 7 ' :· !: - 0 6
P:=!~l,f: H T OEVIAT I 0 i'! 1H 9 5 Cf1i 1 FII)f: i"C c L~\'EL = ?. . 5t.~?.
r.n;• c OF ftCL = . 0600 1 CONC OF L,IJn - = • · t)56 f,
4-t SLOP f: = O . fl3993E - 05LI TER / IWLE - SEC C·H' . T;'.i·:T= 0 . 1660 7 E- OO
T I: F.= 37':-L:-0 . 000 EXP COi'IST==O . lJ.9 8 6!: - :1'~ ' f.' = - 0 . 35~{') 1:-E - 05
TFi E= 76 6BO . OOO EXP CONST=O . l0 7 86 i: - 0':· )(:: '· ==- 0 . 23 A6 '~E - 05
TI! :E=ll fl 080 . 000 EXP COf\!ST = O . l0060E - 04 ) !: ' =- O .l660?.E-0 5
T! ~·;f:=F. J6':·0 . 000 EXP CO!· IS T=0 . 92501!: - 0~ )1;: ' =- O . q507L~E - 06
Tii'l:=?.728oO . OO O EXP CO NST=0 . 8 97 3 1 E.- 05 ) 1: ' =- 0 .57 38 1E-0 6
AVEP.1'. G!: DEV I ATIO N = 0 . 18115E- 05
STf\1··1[!/\R D DEVtA T! Of\l = O. l0575 E- 05
PERCE~ T DEV I AT I ON AT 9 5 CONFIDENC E L EVEL = 25 . 181
-
45
.>J) c:l. ' tP t- :: C'; . l':· 777: - ot: LIT:::~/ ; ;, · ti_'~ - Sl:C C . ~ ,· .. , 'T= 0 . 192Lt:,i:·t·flP
--~
~~T · ~
· ~~=~r~
,r~
J·~·"~,<~l~
·~' i~
' :_
n___r-~
- ~~
:p_
· ~c~r~.i~ls
~
· ~r~
=~0 ~·~
1~7~
3~'~~4~r---~~-
' '~
i· __·_•__
7
Tl i i: =J.l. 5?.l,O . nf"'Q
':' .: - !1 . :5672r: - os
::):P Cf1 1' S T= 0 . 17271 F -r : t~ •1: ' :~ - n . ?.L;9 L~3t: - 05
TT' ': =1 5 7 1)111 . f)nn r:;~p Cf11!S T= 0 . 15 61J3f: - 11 t!. · :~ 1 -: - n . ·~~5H~~'=-06
----:::T-;-J~ · •-:: . 0,.-:'-~:-'-:-~l;_.lc,....
E,....=-::J::-: n .,.n--::E,_,_X;...;,P,..---::C~O~i,..,.:'S:;.,T,;,..=_n.,:.....:..
• r-=-1-::-
l .;:.. • .;:.J. ..;,='..,:,'~,.,;7....;:;:~F=---'',.-':.....
~ _ • : •. "' - 0 • ,; 9 5 5 J. E ..,. 0 6
T Tj ·y =? '~ :: 1: 1, o • o '1 n r= x r co f·! s r =o • 1 57 3 7 r::-" . .i· • · '- ' "' - ' ' • · .' :l o 1 ?. E-o 6
1'.' 1 f:l~i·. c;r- o;;v t t-.TIO: • = Q. 150 36 E-05
ST t\' 1 nt·r~n l.tt:VIfo.T i ni t = o . ;:r.,312t:- 06
F!= ::C f·TT f.ll:VI/· TIU:I ;'..I ~5 COI·•t= I OEi!Ci: U:'/tl = 1 J. . (, :~ z
Cf1 i 'C 'lF P.CL = . 03351 CO l•1C flf , , tJ 'l - = • ' I"\; 9;?
~ S U tPF. = 0 . 16 ?.2R r: -Oitl IT En fi.iflt_ E- S ::c C ; I . y !-I :T = 0 . 3 5~· 1 5 r: -() 1
TJ; :r: = 65:, eo . nno r:;zp CO i! ST = 0 . 1f..,326f: - '> 1~ l ':;:' =-0 . 9 71561: - 07
=
T T: . r: 1 1 3 lt () 0 • 0 0 () E ;~ p c0 I ~ s T ::: 0 • 1 7 1 6 7 r:: - () ~~ " r:I =- ll • ~13 n6 3 E - 0 6
TT I":: = l566(J0 . 0f)O F:;;:r co ;! ST=0 . 1n~ i; 1 ~ - ~ t·. 1.;· = - n .:~5~66E - 06
--~~~~~~~~~~~--~~~~~~~~----~
TT' E=1~l260l) . l')f'\() 1
r:;~p CIJ I· ST=0 . 1 5Q3 <·f: - 'l t~ ·L:' :..~ <).:(90671:-0t)
TTI .I: =?. I\2t~uo . nno EXP CO i iS T=O . l 6'~~ b F. -I'"l 1~ , r: • :=- 1') . ?299 7 E- 06
1'·. '/Ef'.l', \.f:: i)[V lt\TIOII = 0 . 3!1J.8?.E - 06
sr,·. I 'I 'M~n l.lE VI/\Tif1 1J = 0 . 2"~002E - f)G
pr:: '. C!:I'T {)f:V I ATIOf ' 1\T <J5 CO I! Flt)f.i'Ci: u:\1 1: ,_ =
S'WC nr: RCL = . 03155 Cfli !C flF L· 1 1! l - = • · "7$1 ' :·
3J) SU l P F = 0 . 11360F. - 01tU r: :U il(11_E- S!.;C C ·i': 1'-'I'T = 0 . 17 '~?.2!: -01
TI ' ,f: =l1l(, 00 . 0()0 EXP CO I'S T= O .ll'~ 77 f:-')'· t l~· =- O . J.J.f,63E - 06
--~T~T~
i·~
E-==~l~~~3~7~2~C~)·~o~n~n--~~~X~P~C~,O~i~
IS~T~==-O~
·~l~J.~5~3~'~~~~-~0-'~
~ --' ~
1
= - 0 . 17~571::-06
TI I: t:=1<JOilOO . OOO f:XP CLHIS T= O. l111·2Sf-:-()t, I f:' =-n.r,50f!3E - 0 7
'\ '.'l;r.A.(;f: DI:V I /\ TIO.! = O. l l r.7f, r: - or,
THlf.>ER/·. TU I{L I ~; 40 . 7 C
coN c oF 11 c L - · -.-:1~0::--:2::--:_o::--:3=-=--~c::::-(:':":JN:-:-c=--(::::-:JF=--~-
, :-:-:::-
uo----- -.-=o-=9-=a-=a-=o- - - - - - -
f.A SLO PE = v . 3t . 207E - 04LI T ER/I·iULE - SEC COI~STAIH= 0 . 366 1<.Jt: - (t1
T!i-1'1:= ?. 9ilL >. t.O O EXP CONST=O . 3317'~E - 0 't I)EV= 0 . 30330I: - CJ5
T Hi E = 1 0 c.J 0 L d • It 0 0 E X P C0 i'! S T = 0 • 3 8 3 9 1 E- 0 Lt I) EV =- 0 • 2 1 H 5 E- 0 5 't
T I h E = l't 7 6t 11 l • tlO 0 E X P C0 NS T= 0 • 3 7 0 9 't E- 0 4 I) EV =- 0 • H n 6 HA f7 - 0 6
T! iii: = J.<J62i •.J . •t00 EXP C UN ST=0 . 3 5't21E - 0 '~ DEV= 0 .7 fl:596 t: - on
T Hi E = ? '' 0 t3 '1 ;J • t t 0 0 t: XP C0 I'<IS T =0 • 3 6 4 5 1 E- 0 't D EV =- 0 • 2 '• 3 '.i 0 f: - 0 6
AVERA(;£: Ui V I ·. T! Uil = 0 . 14268E - 05
ST/\ i'JD:\i;D [.t:v r t\ T !t'til = 0 . 878491: - 06
PERCEI 1 T 01 V L 1TI O;J t\T 95 Uli'!F i l)EHCt L EVEL = 4 . t1 53
CONC OF RCL = • 101 98 COI!C o:.: bUD- = • 09e80
f6 SLUPE = c . 3 ~ ·0 2 9E -04 LITER/ HULE -S EC COHSTAHT= O. l 3 167c - n1
THlF. = 29U D . •i 00 EX P C ON ST-0 . 35 ~3.:.E - 04 OtV= 0 . 296401:-06
TI I~E = 644'.U . oOO EXP CONST =0 . 333'tuE- 0't DEV= 0 . 24H91E - 05
THa: =l 062t iJ • .,OO EXP CONS T=0 . 3 7'tO::SE - 0't DEV =- 0 . 15743 E- 05
THIE =l 476( O . l OO EXP CU NST= 0 . 3 771 5E- 0't 11EV -- O . l B86 3 E - O~
Ti f.lE = l9SLu . ,O Q EXP CO NST=0 . 347Lt'1E - 04 D tV= O. lO :IOU: - 05
\
AVERAGE Dt VI \ TI Of.l = O . l465 2E - 05
STAND MW I I: VU\TION = 0 . 82 11 8E - 06
PE RCE I'IT Ui V I '< TlUN A T 95 COI,JF IDENCE L EVEL = 4. 5B4
48
T H\ P. ER 1\ Tll R~ ·S 50 • 3 C
c.oNc oF nc L =.-=---.-;rr?ori-o;.-?9~6~----,c--~a"'""r'Tl~c....--,o
~F~L!"'"'urTo,.,.--~--.,...o,...9"~"~"8"8""o-------
~"~"
6's L OPE = 0 . ; 77 )17 E - 04LI T ER /f~OL E- S EC CONSTANT= - 0 . 165 20i.: - Ol
Tlf.IIE = 3?.0't0.000 EXP CO!,JST=0 . 8Lt437E - 0 t~ Dt:V= 0 . 33493E - 05
TIME - 73440.00 1) EXP CONST=O . SH44SE - 04 DEV -- 0 . ~580AE -0 6
TIHE = 91\640.00 0 EXP CONST=0 . 88l50E - 04 OEV =- 0 . 36370E-06
TIME = ll~S ~O.OOO EXP CONST=0 . 8Rl56E-04 DEV=- 0 . 36972E - 06
TH-'tE = l6 3H lJ0uOOO EXP COI\I ST=0 . 8715::SE - 04 DEV- 0 . 633051:: - 06
AVERAGE DEV1AT!UH = O . l0748E - 05
STANOAR!l [Jf:\ I A'd()l! = 0 . 78487E - 06
PERCEin Ul: V ' IH!f1i'l J.\T 95 CO iiJF IOEI'-~CI: LEVEL- 1. 7 H8
~ONC OF RCL :: . 10252 CD I ·~ C OF I:>UO - = . 09H80
SLOPE = u • .. 76 ·:·7E - 04LITER/l·;OLE- SEC Cfli!STA iH= 0 . 7 H66"/t - Ol
TI I·IE= 295 LO .OO n EXP CO NST-0 . 913YuE-04 OEV - - 0 . 37430E-05
T ir,\E= 7tl'J£: 0.001l EXP COI~ST=0 . 9 1 147E - 04 DEV =-0 . 34999E-05
TH.IIE= l 60 9~0.00() EXP CONST=0 . 8388HE - 0 4 DEV= 0 . 375H7E-05
TINE=2012 4 0.00ll EXP CONS T =0 . 90434E - 04 DEV= - 0 . 27868E - 05
AVERAGE OEV JA T ION = 0 . 34471E - 05
STANDARD G~ \ IATION = 0 . 20032E - 05
PERC ENT OI:Vl AT l UN AT 95 COi-.JFIOEHCt:: LEVE L = '~ . 571
CONC OF RC L ~ .1 0085 CO NC OF oUO- = . 09080
~e SLOPE = O . t. 52i ' HE -04LITER/ HOLE - St:C COHSTAin" = 0 . 21?.271:+00
THi E= 2t5ti v0. 0 0 tl EXP CONST-0 . 94744E - 04 DEV - 0 . 54t~llt - 06
TIME = 70200 . 001> EXP CON ST =0 . 98033E-04 DEV=- 0 . 27444E - 05
TINE = 95760.00 Cl EXP CONST=O . l0037E-03 OEV=- 0 . 50835!: - 05
THi E=ll 6640 . 00 C' EXP CONST=0 . 9Y869E-04 OEV = - 0 . '~5H07C:-05
TH1E = l6 0200 . 00ll EXP CONST=0 . 94435E - 04 DEV = 0 . 85 3351: - 06
AVERAGE D~VlATION = 0 . 2 7 612E-05
S T .f\;',JDARil [l E\ I 1\ ·n Oi·l - 0 . 1 66'~1 !: - 0 5
PERCENT LJI:Vl:\T ··· o,,J AT 95 CU r~F IOE I,!C£: LEVEL = 3 . 493
49
TEMPERATU RE IS 59 . 7 C
CONC OF RC L = . 10040 CONC OF ~UO - = . 09880
7A SLOPE = O . l8 3 40E-03LITER/t40 LE- SEC CONS TA NT= - 0 . 640701:: - 0l
THi E= 1656< , 000 EXP CONST=O . l 8043E - 03 OEV = 0 . 296 1t2E - 05
TI I,lE= 2700C. . 000 EXP CO I~ ST=O . l8048E-03 DEV= 0 . 29221E-05
THlE= 7920( ! , 000 EXP CONS T=O . l8104E-03 OEV= 0 . 235f39t.: - 05
THiE= 9064< . 0!10 EXP CONST=O . l 8604E - 03 OEV=- 0 . 34427t -0 5
Tl f-1 E=l130'd . OtJO EXP CONST=O . l79 96E -03 Ut:V= 0 . 3 1 tlt05l: - 05
TH1E= 154UO< · . Oil0 EXP. CONS T= 0 . 10327E-03 DEV= 0 . 131 031: - 06
AVERAGE [IE\ IA.iiOI\I = 0 ~ 25432E -0 5
STANOA:W U l V l t\ TIOI'l = O. l 2463 E- 05
PERC E!'l T UE \' I AT I ON AT 95 cu ;,JF I OEf.JCE LEVEL = 1. 359
CONC OF RCL = , 10129 CONC OF GUU- = . 09HHO
78SLOPE = 0. 19206E - 03LITER/i·10LE - SEC CDhSTA!·JT= - 0 . 27<.J20t - !J0
T I foil E = 2 6 2 Uu • 0 0 0 =
EX P C0 ~JS T 0 • l 7 0 3 ~ E- 0 3 =
I) EV 0 • 1 3 7 4 1 E - 0 1t
TI NE= 5400· •. 0•)0 EXP COHST = O . l7256E-03 DEV= 0 . 19Lt97t-I'J 1+
TI HE= 506H oi , QOO EXP COi'·l ST=O.l 9 2 36E - 03 ucV =- 0 . 2979:.51: - 0f)
Tll"E= 7 8 1t B·l , OOO EXP C ONS T= 0 . 20 1 't~E-03 OEV= - 0 . 93~>91E - n~;
T Hl E = 9 0 2U 1 • 0 0 0 =
E >: P C0 f'l S T 0 • 1 9 0 4 0 E- 0 3 =
D EV 0 • l 5 f\1 U:- n "l
TH·1 E=ll 26 0 >. 000 EXP CONS T= O . l 8't45E - 03 DEV= 0 . 76l3'tl: - o:>
AVERAGE DE ' I A TIO N = 0 . 86815E- 05
STA!'lOJ\RD l.J :viA Ti mJ = O . tt8890E - 05
PERCE~:T t)l:. ! I / TIOr'l AT 95 COI·IFIOEI·!Cc LEVEL = 5 . 091
50
TF''PE~ /\ TU :~ E IS 69 . f~ C
JA Cr J· 'C OF RC L = . 10017 COi!C l1F '-'l!ll- = • )<:.·H: O
SLOPE = 0 . '~0685E -03LITEK/ iiO L E-SEC C(l i ~T id'H= 0 . 39645E+O
TI! : E= 17532 . 000 EXP COHST=0 . 40222E - 03 D{ .t : 0 . '~6277E - 05
Tii iE = 26100 . 000 EXP CU:!S T=0 . 4314UE- 0 3 Ill 1 =- 0 . 2. '~5.491: - 04
TT :iE = 3556 1'3 . 000 EXP CtH·!ST=0.41731F.-03 D1 ··.'=-0 . 10464E-0'~
T!; 't: = 't06t;O . OOO EXP Cuf.IST=0 . 4'~0 56 e-- 03 01 ' =- 0 . 337 12E-0'~
T I :• E= 51300 . 000 E;~p C Oi·IST=0 . '~0 059E - 03 Oi· '·/= 0 . 62547E - 05
=
J'. \f E n AGE [) E V U\ T J ("l i I 0 • 1 59 2 1 E- 0 't
STA I·111AP.D OEV!ATIOH = 0 . 97703E-05
PF.HCF. f·! T DEVIATION 1\T 95 COI·! FIDE HCl: LEVE t_ ::- l; . 80 3
1~COi ! C OF RC L = . 10003 COI-!C Or b UO- = . n<?8RO
SL OPE = 0 . 4332 1 E- 03 LITER/M OLE - SEC SOi STANT= - 0 . 25094E-C
Tii·i E= 1666B . OOO EXP COI>JST=0 . 406 U7E - 03 i), V = 0 . 26338E - 04
TIHE= 25200 . 000 EXP CONST=0 . 41574E-03 DI V = 0 . 17475E-04
TiliE= 34920 . 000 EXP CONST = 0 . 44633E-03 Q j V=-0 . 13115E- 04
TI NE = 50832 . 000 EXP CU NST = 0 . 42176E - 03 D V= 0 . 11457E - 04
AVERAGE DEVIAT I ON = O.l7 096E - 04
STANDARD DEV I AT I ON = O. l0418E - 04
PERCEN T DEVIAT I ON AT 95 CONFIDEHCE LI:Vl:L : : 't . 809
VITA