EXPERIMENTAL - Shodhgangashodhganga.inflibnet.ac.in/bitstream/10603/74918/7/07_chapter 3.pdf · The esters were decomposed using 10% sodium hydroxide solution. ... culated from the

CHAPTER III

EXPERIMENTAL

MATERIALS

A.R. sodium chloride, sodium nitrate, sodium bromide,

sodium sulphate and the lithium sulphate were dried at 150° C

and kept in a desiccator. A.R. lithium perchlorate

(an�ydrous) was dried under vacuum in an Abderhalden

drying pistol over,

P2o5•

Sodium hydroxide used for titration was prepared

free from sodium carbonate by standard methods(119) and was

standardised against A.R. pottassium hydrogen phthalate (120).

Substituted Benzenes

(Substituents - Me, Et, F, Cl, Br, OCH3)

Toluene, ethyl benzene, fluoro benzene, chloro benzene,

bromo benzene, and anisole used were BDH quality.

p-Substituted acetophenones

(Substituents - Me, Et, F, Cl, Br, OCH3

)

All the acetophenones were prepared by Friedel

Crafts acylation of the corresponding substituted benzene

( 1 21 , 122,123) •

12.-Meth(9yl acetophenone

12.-Ethyl acetophenone

12.-Methoxy acetophenone

12.-Fluro acetophenone

12.-Chloro acetophenone

12.-Bromo acetophenone

b.p.(C0)

111.5/11 mm

173-174/?0mm

145-148/35mm

65-66/20 mm

127-29/40 mm

129-30/11 mm

1-Phenyl ethyl alcohol used was BDH quality.

1..::iP-R-phenyl) ethyl alcohol

(R - Me, Et, F, Cl, Br, OCH3)

59

39

51

The alcohols were prepared by the sodium borohydride

reduction of the corres.ponding ketones (125). The alcohols

were purified by fractional distilation in vacuo (124).

1-(12.-methoxy phenyl) ethyl alcohol was prepared by reducing

the corresponding ketone and was directly used for the pre-

paration of the phthalate as the impure sample polymerises

on distihation (126). All the alcohols were purified

through their acid phthalates. The esters were decomposed

using 10% sodium hydroxide solution. The regenerated alcohols

were further purified by fractional distillation in vacuo.

1::.{_p-R-phenyl) ethyl hydrogen succinates

(R - H, Me, Et, F, Cl, Br, OCH3

)

The hydrogen succinates were prepared by methods

similar to one described by Eli el et. al. ( 127) •

60

1-(ft-methoxyphenyl)ethyl hydrogen succinate was prepared

by methods similar to one described by Kenyon et. al. (126).

The esters were pur�fied through their sodium salts. The

chloro and bromo substituted acid succinic esters were

further purified by repeated recrystallisation from benzne

petroleum ether (40-60° C) mixture. The esters were dried

in vacuo.

1-(Q-R-phenyl)ethyl hydrogen succinates

R

H

Me

Et

F

Cl

Br

MP° C

56 .. 57

77-78

.

Mol. wt. Calcd. Found

(Ti trimetric)

222 223.0

236 236.8

250 252.0

240 243.0

256.5 256.8

301 .o 30116

268 270.0

KINETIC TECHNIQUE

(All volumetric apparatus used were calibrated)

Titrimetric method

Accurately weighed quantities of tµe ester and the

respective salts were transferred into a 250 ml standard

flask with the aid of the solvent ·and dissolved by shaking.

61

10 ml aliquots were pipetted out into clean and dry ampoules

(which passed the B.P. test for limits of alkalinity) (128).

and the ampoules were sealed. The sealed ampoules were

immersed together in a thermostat and one ampoule was

shaken vigorously for two minutes so that the contents

of the ampoule reached the thermostat temperature. This

ampoule was taken out at a known time and suddenly chilled

to kill the reaction. It was washed thoroughly in tap water,

rinsed in distilled water and broken in a stout pyreJU glass

vessel containing ice cold distilled water. The contents

in the pyrex1-1 glass vessel were titrated against wtandard

alkali using phenol red as indicator (a few drops of a

0.4% solution of phenol red was used as the indicator).

The quantity of indicator used was kept constant to minimise

indicator error. This was the �ero reading. At suitable

intervals one ampoule after another was taken out from the

thermostat and the succinic acid formed estimated by

standard NaOH.

The infinity titre for comparatively faster reactions

were taken after keeping the sealed ampoules in the thermo

stat for a period equivalent to ten half lives and was the

mean of two concordant values. For slow reactions this

method was impracticable. Therefore the infinity titre

was calculated from the initial titration before heating

62

and making the necessary correction for the slight acidity

of the solvent developed at high temperature. This method

was checked in a sufficient number of runs and found to be

satisfactory o

A conventional thermostat ( ± .08°C) was used for

rate measurements. The temperature of the thermostat

was controlled using Jumo contact thermometers.

The reaction followed a first order rate law and

the rate constants were calculated according to the equation,

2.303 a

t1 = t log10 a::i where t is the time in seconds 'a'

is the titre value corresponding to the initial concentration

of the ester and a-xis the titre value corresponding to the

concentration of the ester remaining unhydrolysed at time 't'.

All the first order rate coefficients given in this thesis

are in reciprocal seconds. The mean value of�, was cal-

culated by least square method. All runs were conducted

at least in duplicate and the mean values of rate constants

taken for further calculations.

The thermodynamic quantities of activation parameters

were calculated from tobsd values at four to six temperatures

with 20 to 25 ° range. The activation energies were cal

culated from the graphs and by the method of least squares.

The probable errors and correlation coefficient (129) were

,. '

63

calculated by the method of least squares. The accuracy

Of AH* + -1 :t:Li is -•2 k.cal mole and of .6..S is ± .1. e. u.

The solubility of the ester in different concentra-

tions of the salt solutions at 35 ° C was obtained. Saturated

solutions were prepared by stirring the solution containing

excess of the ester for 12 to 15 hours. No solvolysis of

the ester was found during this period.

64

TABLE 12

EFFECT OF SALT IN THE HYDROLYSIS OF 1-(£-CHLOROPHENYL)

ETHYL HYDROGEN SUCCINATE IN WATER

Temp: 100°C (NaCl)= 0.01 M (ester)= 0.008M

Titres are expressed as ml of 0.00776N NaOH per 10 ml

of reaction mixture.

------------------------------------------------------------

t Titre log(a-x) 4 ( -1) 10 �1

sec

------------------------------------------------------------

0 5.42

5700 5.96 o.6474 0.201

6300 6.04 o.6395 0.201

8400 6.18 0.6253 0.198

9900 6.30 0.612s 0.197

11 700 6.44 0.5977 0.196

13500 6.56 0.5845 0.193

1 6800 6.84 0.5514 0.200

18000 6.92 0.5416 0.200

1 9800 7.06 0.5237 0.199

20700 7 .1 0 0.5185 0.1 99

21600 7 .18 0.5079 0.201

Infinity 1 O.L}O

1 o4t

1 (sec -1 ) (Least Square Method) = 0.202

Duplicate gave = 0.201

------------------

------------------

----------------

--------

65

TABLE 13

EFFECT OF SALT IN THE HYDROLYSIS OF 1-(Q-CHLOROPHENYL)ETHYL

HYDROGEN SUCCINATE IN WATER

Temp: 100°C (NaCl)= 0.025M (ester)= 0.008M


of the reaction mixture

------------------------------------------------------------

t Titre log(a-x)

------------------------------------------------------------

0 6.90

1800 7 .12 0.7839 0.197

4200 7.42 o. 7619 0.205

5400 7.56 0.7513 0.205

7800 7.80 0.7324 o.198

9300 7.92 0.7226 0.190

11100 8.14 0.7042 o.198

12900 8.34 0�6866 0.201

14400 8.46 o.6758 0.198

16200 8.64 o.6590 0.200

17700 8.76 o.6744 0.198

19200 8.88 o.6355 0.197

Infinity 13.o20

1 o4�1 (sec-1 ) (Least Square Method) = 0.197

Duplicate gave = o.197

------------------------------------------------------

------

66

TABLE 14



�emp: 100°C (NaCl)= 0.05M (ester)= 0.0078M

Titres are expressed as ml of 0.00325N NaOH per 1 0 ml of the reaction mixture.

------------------------------------------------------------

t Titre log(a-x) 4 ( -1) 10 t1

sec ------------------------------------------------------------

0 12064

3480 13.44 1 .0237 0.21 0

5520 13.92 1 .0033 0.21 7

7020 14.20 0.9912 0.211

9300 14.70 0.9685 0.215

11100 1�.04 0.9523 0.214

12600 15.30 0.9395 0.212

14940 15.70 0.9191 0.210

18000 16.26 0.8887 0.213

21900 16.84 0.8549 0.211

23700 17 .14 0.8363 0.213

Infinity 24.oo

1 o4t

1 (sec -1) (Least Square Method) == 0.213


-----------------�----------------------�

-------------------

67

TABLE 15,

EFFECT OF SALT IN THE HYDROLYSIS OF 1-(E-CHLOROPHENYL)ETHYL


Temp: 100° C (NaCl) = 0.1M (ester)= 0.0078M

Titres are expressed as ml of 0.00325N NaOH per 10 ml of the reaction mixture.

. .

------------------------------------------------------------

t Titre log(a-x)

------------------------------------------------------------

0

5880

8880

10860

13500

15600

19800

21300

Infinity 4 -1)10 �1

(sec

Duplicat�

12.40

13.64 1 .0153 0.193

14.20 0.9912 0.190

1 L�.56 0.9750 0.192

15.04 0.9523 0.191

15.44 0.9325 0.196

16.14 0.8954 0.198

16.30 0.8865 0.194

24.oo

(Least Square Method) = 0.196

= 0.194

-------------------------------

--------------------

---------

68

TABLE 16

EFFECT OF SAI1' IN THE HYDROLYSIS OF 1-(Q-CHLOROPHENYL)ETHYL


Temp: 100°C (NaCl)= 0.15M (ester)= 0.1012M

Titres are expressed as ml of 0.00775N NaOH per

10 ml of the reaction mixture.

------------------------------------------------------------

t Titre log(a-x)

------------------------------------------------------------

0 7.96

f$44o e.94 o.8156 0.187

9000 9.08 0.8012 0.180

10860 9.34 0.7882 0.187

12600 9.52 0.7752 0.185

14400 9.70 o. 7619 0.183

16200 9.92 0.7451 0.186

18000 10.08 0.7324 00184

19800 10.24 0.7193 0.183

21720 10.46 0.7007 0.186

Infinity 15.48

1 o4�1 (Sec-1) (Least Square Method) = o.1 a5


----------------------------------------------------

----�---

69

TABLE 17



Temp: 1 00°C (NaCl)= 0.25M (ester)= 0.008M


------------------------------------------------------------

t Titre log(a-x)

------------------------------------------------------------

0 6.00

3600· 6.36 0.7059 0.1 90

5400 6.54 0.6902 0.1 94

7260 6.70 o.6758 0.190

9000 6.86 0.6609 0.191

1 0800 7.02 o.6454 0.1 92

12600 ,.16 o,6314 0. 1 91

1 4580 7.34 0.61 2s 0.1 94

1 6320 7.46 0.5999 0.192

18000 7o60 0.5843 0.194

20400 7.76 0.5658 0.1 92

Infinity 11.44

4 ( -1) 1 0 t1

sec (Least Square Method) = 0. 1 93

Duplicate gave =.0.192

-----------------------------------------

-------------------

70

TABLE 18

EFFECT OF SALT IN THE HYDROLYSIS OF 1-(£-CHLOROPHENYL)ETHYL

HYDROGEN SUCCINA'rE IN WATER

Temp: 100° C (KCl) = 0.05M (ester)= 0.008M

Titres are expressed as ml of 0.00774N NaOH per 10 ml of' reaction mixture.

-----------------------------------------------------------


sec

-----------------------------------------------------------

0 6.06

1800 6,24 0.7292 0 .1 829

3660 6.42 0�7143 0 .1838

5160 6.56 0.7024 O .1834

6900 6.72 o.6884 0 .1840

9480 6.94 o.6684 0 .1 824

10800 7.06 o.6571 0.184

12600 7.22 .o.6415 0.182

15000 7.38 0.6253 0 .1 81

1 6500 7 .50 0.6128 0.1 82

20100 7.76 0.5843 0.182

21600 7.88 0.5705 0.184

4 ( -1)10 t1

sec (Least Square method) = o.183


---------------------------------------

------------------

71

TABLE 19


HYDROGEN SUGGINATE IN WATER

Temp: 100° C (ester)= 0.008M

Titres are expressed as ml of 0.00773N NaOH per 10 ml of reaction mixture.

----------------------------------------------------.--------

t Titre log(a-x)

------------------------------------------------------------

0 4.64

10800 5.48 0.5563 0.194

12600 5o60 0.5416 0.193

14400 5.70 0.5289 0.190

16200 5.84 0.5105 0.194

18000 5.92 o.4997 0.190

19800 6.02 o.4857 0.190

21 600 6.16 o.4654 0.194

23100 6.24 o.4533 0.194

Infinity 9.08

1 o4t

1 (sec-1) (Least Square Method) = 0.192


----------------------------------------�-------------------

72

TABLE 20



Temp: 100° C (ester)= 0.008M



------------------------------------------------------------

t Titre log(a-x)

------------------------------------------------------------

0 4.68

5400 5.10 0.5635 0.201

6900 5.22 0.5490 0.206

9000 5.36 0.5315 0.203

10800 5.46 0.5185 0.199

12600 5.60 o.4997 0.203

16440 5.84 o.4654 0.204

20700 6.08 o.42s1 0.203

24000 6.28 0.3945 0.207

Infinity 8.76

4 ( -1)10 �1 sec (Least Square Method) = 0.209·


------------------------------------------�------

-----------

73

TABLE 21



Temp: 100°C (ester)= 0.008M



------------------------------------------------------------

t Titre log(a-x)

------------------------------------------------------------

0 5.08

7200 5.68 0.5933 0.198

9120 5.84 0.5752 0.200

10800 5.94 0.5635 0.195

12660 6.06 0.5490 0.193

14400 6.18 0.5340 0.194

16200 6.30 0.5185 0.194

18000 6.42 0.5024 0.196

21600 6.66 0.4683 0.197

In�inity 9.60 4 ( -1

)10 �1 sec (Least Square Method) = 0.196


-------------------------------------

--------------

---------

74

TABLE 22



Temp: 100° C (ester)= 0.008M

Titres are expressed as ml of 0.00778N NaOH per 10 ml of reaction mixture .

------------------------------------------------------------

t Titre log(a-x) 4 ( -1) 10 �1 sec

------------------------------------------------------------

0

5400

7200

9000

10800

12600

14400

16200

18000

19800

21900

23400

24900

Infinity 4 -1)10 �1 (sec

Duplicate

5.54

6.06 o.6866 0.188

6.22 o. 6721 0.188

6.36 0.6590 0.184

6.52 o.6435 0.186

6.68 0.6274 0.189

6.82 o.6128 0.188

6.94 0.5999 0.186

7.e6 0.5866 OJ 185

7 .18 0.5729 0.184

7.36 0.5514 0.187

7.44 0.5416 o.186

7.54 0.5289 o.1e7

10.92


= 0.187

--------------------------------�------------�--------------

75

TABLE 23

0 EFFECT OF SALT IN THE HYDROLYSIS OF 1-(:12.-CHLORJ'HENYL)ETHYL


T emp: 100°C (ester)= 0.008M


---------------�--------------------------------------------

t Titre log(a-x)

------------------------------------------------------------

0 6.32

7200 7, 10 0.7177

9000 7.30 0.7007

11400 7.50 o.6s30

12600 7.64 o.q702

14400 7.82 o.6532

15900 7.94 o.6415

17400 8.02 o.6335

19200 8.20 o.6149

Infinity 12.32 4 -1)10 t1 (sec (Least Square Method) = 0.195

· Duplicate gave = .0.196

0.194

0.19s

0.192

0.197

0.199

0.190

0.192

0.196

------------------------------------�

-----------------------

76

TABLE 24

EFFECT OF SALT IN THE HYDROLYSIS OF 1-(�-CHLOROPHENYL)ETHYL


Temp: 100°C (NaBr) =.025M (ester) =.008M

Titres: are expresse<fas ml of 0.00778N NaOH per 10 ml


------------------------------------------------------------

t Titre log{a-x) 4 ( -1) 10 t1

sec

------------------------------------------------------------

0 4.70

7200 5.14 0.5821 0.154

9300 5.28 0.5658 0.157

10800 5.36 0.5563 0.156

12900 5.46 0.5441 0.153

16200 5.64 0.5211 0.154

18000 5.76 0.5051 0.159

19800 5.84 o.4942 0.157

21600 5.90 o.4857 0.153

23700 6.00 o.4713 0.154

26100 6.14 o.4502 0.158

Infi nity 8.96

1 o4t

1 (sec -

1 ) (Least Square Method) = o.157

Duplicate gave =·0.157

-----------------------------------------

-------------------

77

TABLE 25



Temp: 100°C (NaBr) = 0.05M (ester)= 0.008M


------------------------------------------------------------

t Titre log(a-x) -------

-----------------------------------------------------

0 4.26

5400 4.64 0.5658

7200 4.76 0.5514

9000 4.88 0.5366

1 0500 4.98 0.5237

13500 5 .. 16 o.4997

15000 5.24 o.4886

16800 5.34 o.4742

18600 5.42 o.4624

20100 5.54 o.4440

22200 5.62 o.431 4

Infinity 8.32

4 -1)1 0 t1 (sec (Least Square Method) = 0.185


o.1 s2

0.183

0.184

0.185

o.1s6

0.184

o.184

0.181

o.1 ss

0.1 84

------------------------------------------

------------------

78

TABLE 26

EFFECT OF SALT IN THE HYDROLYSIS OF 1-(:e_-CHLOROPHENYL)ETHYL


Temp: 100 °C (NaBr) = 0.1 5M (ester)= 0.008M

Titres are expressed as ml of O o 00783N NaOH per

10 ml of reaction mixture.

------------------------------------------------------------

I t Tit:ee log(a-x) 4 ( -1) 10 t1

sec

------------------------------------------------------------

0 3.70

5400 4.04 o.4829 0.196

7200 4.14 o.4683 0.194

9300 4.26 o.4502 0.195

10800 4.34 o.4378 0.194

12600 4.42 o.4249 0.190

14400 4 o52 o.4082 0.193

16200 4.60 0.3945 0.1 91

18000 4.70 0.3766 0.195

Infinity 7.08

1 o4t



---------------�----------------------------��--------------

79

TABLE 27



Temp: 100° C (NaBr) = Oo25M (ester)= 0.008M


-------------------------------------------------------------

t Titre log(a-x) -------------------------------------------------------------

0 4.74

3600 5.02 o.60855400 5 .16 0.59337500 5.30 0.57759000 5.40 0.5658

10800 5.50 0.553912600 5.64 0.536615000 5.78 0.518515900 5.86 0.5079

18000 5.94 o.496919500 6.04 o.482922200 6.20 o.4594

24300 6.30 o.4440

26400 6.40 o.42s1

Infinity 9.08

1 o4t1 (sec-

1f (Least Square Metil.od) = 0.184


Oo,,196 0.188 0.184

0.184 o.1s20.1840.183o.1870.1830.183o.1 s40.1840.184

------------�---------------------------------------

---------

80

TABLE 28

EFFECT OF SALT IN THE HYDROLYSIS OF 1-(:2.-CHLOROPHENYL)ETHYL


Temp: 100° C (LiCl04) = 0.01M (ester) = 0.008M


t Titre log(a-x)

-----------------------------------------------------------

0 4.94

5400 5o40 0.6355

8100 5.60 o.6149

9600 5.70 0.6042

11100 5.84 0.5888

12900 5.94 0.5775

14400 6.06 0.5635

15900 6;14 0.5539

19500 6.36 0.5263

Infinity 9.72 4 -1)10 �1 (sec (Least Square Method) =

Duplicate gave =

o.187

o.1s3

0 .181

0.183

o.182

0.185

0.182

0.181

0.180

0.181

--------------------------�-----------

�----

-----------------

81

TABLE 29



Temp: 100° C (ester)= o.008M


-----------------------------------------------------------

t Titre log(a-x) 4 ( -1) 1 O �1 sec

------------------------------------------�----------------

0 9.06

10800 10. L�8 0.8476

12600 10. 70 0.8338

16200 11.10 0.8075

18240 11.32 0.7924

19800 11050 0.7796

21900 11.70 0.7649

22920 1111;78 0.7589

Infinity 17.52

4 -1)10 �1 (sec (Least Square Method ) = 0.170


0.170

0.171

0.170

0.170

0.112

0.171

0.170

--------------------�----------------------

-----------------

82

TABLE 30

EFFECf OF SALT IN THE HYDROLYSIS OF 1 ';'(:Q.-CHLOROPHENYL)ETHYL


Temp: 100° C (LiCl04

) = 0.1M . (ester) = 0.008M


------------------------------------------------------------

t Titre log(a-x) 4 ( -1 1 0 �1 sec )

------------------------------------------------------------

0 7 .72

5400 8.40 0.8248 0.180

7320 8064 0.8089 0.1 83

10920 9.04 0.781 0 o.1 s1

12790 9.24 0.7664 0.181

1 4400 9.40 0.7543 0.1 80

16200 9.60 0.7388 0.1 82

18000 9,.78 0.7243 o.183

1 9800 9.98 0.7076 0.185

23400 1 0.30 o.6794 0.1 85

Infinity 15.08

1 04t

1(sec-1 ) (Least Square Method) = o.188


-----------------------------------------------------------

-.

83

TABLE 31

EFFECT OF SALT IN THE HYDROLYSIS OF 1-(p-CHLOROPHENYL)ETHYL


Temp: 100°C (LiCl04

) = 0.25M (ester)= 0.008M



------------------------------------------------------------


sec

------------------------------------------------------------

0 4.88

7400 J.46 0.6128 0.184

9000 5.58 0.5999 0.180

10800 5.72 0.5843 0.183

. 12600 5.86 0.5682 0.186

14400 5.98 0.5539 o.186

16200 6.08 0.541 6 0.183

18180 6020 0.5263 0.183

19800 6.30 0.51 32 o.1 s3

21000 6.40 o.4997 0.1 86

Infinity 9.56

1 o4t

1 (sec -

1) (Least Square Method) = 0.186

Duplicate gave = 0.1 87

------------------------------------------------------------

84

TABLE 32



Temp: 100° C (ester) =·0.008M


---------------------------------------�--------------------t Titre log(a-x)

------------------------------------------------------------0 4.14

5400 4.38 0.5635 0.11 s

7200 4 . 46 0.5539 0.120

9300 4.56 0.5416 0.123

10800 4.64 0.5315 0.122

13200 4.72 0.5211 0.122

15300 4.80 0.5105 0.121

17100 4.88 o.4997 0.123

18900 4.94 o.4914 0.121

20700 5.00 o.4829 0.120

22800 5.08 o.4713 0.121

26100 5.20 o.4533 0.122

Infinity 8.04

104�1 (sec-1) (Least Square Method) = 0.122


-----------�------------------------------------------------

85

TABLE 33



Temp: 100° C (ester):::0.008M


------------------------------------------------------------

t Titre log(a-x) --------------------------------------�---------------------

0 4.74

7500 5.16 o. 6191

9000 5.24 0.6107

10800 5.32 0.6021

12600 5.42 0.5911

14400 5.50 0.5821

16200 5.58 0.5729

18000 5.68 0.5611

19800 5.76 0.5514

21600 5.84 0.5416

23100 5.90 0.5340

Infinity 9.32

1 o4�1 (sec -1) (Least Square Method) = 0.127


0.128

0.128

0.126

0.128

0.126

0.125

0.12s

0.127

0.127

Oo 127

-------------------------------�----------------------------

86

TABLE 34

EFFECT OF SALT IN THE HYDROLYSIS OF 1 -(2-CHLO ROPHENYL)ETHYL


Temp: 100°C {ester)= 0.008M


of reaction mixture$.

-----------------------------------------------------------

t Titre log(a-x)-----------------------------------------------------------

0 4.88

3600 5.06 0.621s 0.120

5400 5 .16 0.6107 0.123

7500 5.28 0.5977 0.125

9000 5.34 0 .. 5911 0.124

10800 5.42 0.5821 0.123

12600 5.50 0.5729 0.122

14400 5.60 0 .5611 0.125

16200 5 .. 68 0.5514 0.125

18000 5 .. 76 0.5416 0.125

19800 5.84 0.5315 0.126

22200 5 .. 94 0.5185 0.126

Infinity 9.24

1 o4t1

(sec-1) (Least Square Method) = 0.126


----------�-------------------------------------------------

87

TABLE 35:

EFFECT OF SALT IN THE HYDROLYSIS OF 1-(p-CHLORBPHENYL)ETHYL





-----------------------------------------------------------

t Titre log(a-x)

-----------------------------------------------------------

0 5.06 •

3600 5.24 o.6739 0.104

6300 5.38 0.6609 0.107

7200 5.40 0.6590 0.100

9240 5.50 o.6493 0.102

10920 5.60 o.6395 0.107

12600 5.68 o.6314 0.108

14400 5. 78 0.6212 0.110

16200 5.88 0.6107 0.110

18000 5.92 0.6064 0.107

19800 6.00 0.5977 0.108

Infinity e.96

104t1 (sec-1) (Least Square Method) = 0.110

Duplicate = 0.110

----------

--------------

----------------

-------------------

88

TABLE 36

EFFECT OF SALT IN THE HYDROLYSIS OF 1-(£_-CHLOROPHENYL)ETHYL




------------------------------------------------------------

t Titre log(a-x) 104�1 (sec-1)

------------------------------------------------------------

0 5.06

1800 5 .16 o.6435 0.124

7500 5.44 0�6128 0.124

9000 5.54 0.6042 0.125

12000 5.70 0.5866 0.127

14100 5.80 0.5752 0.127

15300 5.86 0.5682 0.128

16800 5.92 0.5611 0.126

18000 5.96 0.5563 0.124

19800 6.02 0.5490 0.121

Infinity 9.56 4 ( -1) 10 �1 sec (Least Square Method) = 0.125


--------------------------------------------------

----------

89

TABLE 37

EFFECT OF SALT IN THE HYDROLYSIS OF 1-(12.-CHLOROPHENYL)ETHYL


': r.>:; Temp: 100° C (est�r) = 0.008M


10 ml of reaction mixture.

------------------------------------------------------------

t Titre log(a-x) 4 ( -1)10 !f1 sec ,.

------------------------------------------------------------

0 5.60

7200 6.02 o.6454

9000 6.12 o.6355

10500 6.20 0.6274

12300 6.32 0.6149

14400 6.42 0.6042

16200 6.50 0.5955

18600 6.64 0.5798

20700 6.72 0.5705

23400 6.84 0.5563

Infinity 10.44

4 -1)10 !f1 (sec (Least Square ·Method) = 0.127

Duplicate gave = 0.12s

0.126

0.126

0.126

0.130

0.129

Oo127

0.130

0.127

0.123

-----------------------------------------

-------------------

90

TABLE 38

EFFECT OF SALT IN THE HYDROLYSIS OF 1-(12.-CHLOROPHENYL)ETHYL


Temp: 100° C (ester)= 0.007M

Titres are expressed as ml of 0.0071N NaOH per 10 ml of reaction mixture o

-----------------------------------------------------------

t Titre log(a-x) 4 ( -1) 10 �1 sec ------------------------------------------------------

-----

0 5.34 1800 5.48 o.6955 0.155 7200 5_.88 0.6590 0.155 9000 6.oo 006474 0.154

11100 6.14. o.6335 0.154 12600 6.26 0.6212 0.156

14760 6.38 o.6os5 0.155 ' ··

15900 6.44 0.6021 0.153

17700 6.56 0.5888 0.155

19200 6.64 0.5798 0.154

20700 6.72 0.5705 0.153

21600 6.80 0.5611 0.156

23700 6.90 0.5490 0.154

Infinity 10.44 4 ( -1)10 !!1 sec (Least Square Method) = 0.154

Duplicate gave = o":154

--------------------------------------

---------------------

91

TABLE 39



Temp: 100° C (ester)= 0.008M


10 ml of the reaction mixture.

--------------------------�--------------------------------

t Titre log(a-x) 4 ( -1) 1 O !f1

sec

_________________________________________________________ ..,_

0 4.14

5400 4.40 O .5051 0.148

7200 4o48 o.4942 0.146

11700 4.70 o.4624 0 .. 150

13800 4.78 o.4502 0.148

15600 4.86 o.4378 0.149

17100 4.90 o.4314 0.145

20700. 5.04 0. 1+082 0.146

24600 5.20 0.3808 0.1 48

Infinity 7.60

1 0 4t1

( S e C -1 ) (Least Square Method) = 0.148

Duplicate gave = 0.147 '

-----------------------------------------------

------------

!

92

TABLE 40



Temp: 100° C (ester) 0.008M


of the reaction mixture.

t Titre log(a-x)

0 7.42

1800 7 .60 0.8274

7500 8.16 0.7896

9900 8.36 0.7752

11280 8.48 0.7664

13080 8.66 0.7528

14100 8.70 0.7497

16200 8.90 0.7340

19800 9.20 0.7093

21600 9.32 0.6990

Infinity 14.32

4 -1) 10 �1 (sec (Least Square Method) = 0.150


4 ( -1) 10 �1 sec

0.146

0.151

0.148

0.148

0.151

0.146

0.149

0.150

0.150

---------------------------------------------�-------------

93

TABLE 41

EFFECT OF SALT IN THE HYDROLYSIS OF 1-(2-CHLOROPHENYL)ETHYL





_____________________________________________ , ________________ _

t T'itre log(a-x) 4 ( -1) 1 0 t1

sec

0 7.72

3600 8.14 0.8537 0.1 58

7200 8.52 0.8299 0.1 56

9000 8.70 0.81 82 0.1 54

10800 8.92 0.8035 0.160

16200 9.44 0.7664 0.159

18000 9.56 0.7574 0.155

19800 9.70 0.7466 0.154

21600 9.88 0.7324 0.1 56

23100 10.04 0.71 93 0.158

Infinity 15.28

1 0 4t1 ( S e C -

1 ) (Least Square Method) = 0.156.


------------------------------------------------------��---

94

TABLE 42

E FFECT OF SALT IN THE HYDROLYSIS OF 1 -(12.-CHLOROPHENYL)ETHYL


Temp: 1 00 ° C (ester)= 0.008M



t Titre log(a-x) ------------------------------------------------------------

0

5400

9000

1 3500

14400

1 6200

18000

19800

21 600

22800

Infinity

1 o4t1

(s ec-1 )

Duplicate gave

6.54

7.00

7.28

7.60

7.68

7,80

7.92

a.o4

8.16

8.26

12.32

(Least

0.7259 o.1 54

0.7024 0.1 52

006739 0.1 50

o.6665 0.1 53

o.6551 0.1 52

o.6435 0.1 52

o.6314 0.1 52

o. 61 91 0.1 52

o.6085 0.155

,.I.·

Square Method) = 0.153

= 0 .153

------------------------------------------------------------

95

TABLE 43



Temp: 1 00°C (ester)= 0.008M


----------------�------------------�-----------------------

t Titre log(a-x) 4 ( -1)1 0 t1

sec .·

--------------------�----------------------�---------------

0 6.40

5400 6.84 0.7356 0.1 44

7500 7.00 0.7226 0.1 44

9300 7 .1 2 o. 71 60 0. 1 44

12300 7.36 0.6929 0.1 45

14100 7 .1+6 o.6s30 0.1 41

1 5900 7.58 . o.6721 0.1 41

18000 7.74 o.6571 0.1 44

19800 7.86 o.6454 0.1 44

21600 7 .9s· o.6335 0.145

22500 8.04 o.6.,.74 0.145

Infinity 12.28 4 ( -1 )1 0 �

1 sec (Least Square Method) = 0.145


-----------------------------------------------------------

96

TABLE 44

HYDROLYSIS OF 1 -PHENYLETHYL HYDROGEN SUCCINATE IN WATER

Temp: 85° C (ester)= 0.018M


------------------------------------------------------------

t Titre log(a-x) 4 ( -1) 10 !f1 sec

0 7.92

3600 8.1 2 0.8376 0.0793

5400 8.22 0.831 2 0.0802

7200 8.32 0.8248 0.0806

9000 8.42 0.81 82 0.0814

10800 8.50 0.8129 0.0791

1 2600 8.60 0.8062 0.0801

14400 8.70 0.7993 0.0811

15600 8076 0.7952 0.0810

1sooe 8.88 0.7868 0.0808

Infinity 15.00

1 o4t

1 (sec -1) (Least Square Method) = 0.0811

Duplicate fgave = 0.0810

--------------------------------------------�--------------

97

TABLE 45

HYDROLYSIS OF 1-PHENYLETHYL HYDROGEN SUCCINATE IN WATER




-----------------------------------------------------------


-----------------------------------------------------------

0 7.94

5400 8.42 0.8209 0.130

6900 8.56 0.8116 0.133

8400 8.70 0.8021 0.135

11400 8.92 0.7868 0.131

12900 9.06 0.7767 0.133

14400 9.18 0.7679 0.133

15900 9.30 0.7589 0.134

17400 9.44 0.7451 0.137

18900 9.56 0T7356 0.137

20100 9.64 0.7292 o.136

Infinity 15.04

104�1 (sec-1) (Least Square Method) = 0.139


---------------

--------------------

-------------------------

98

TABLE 46


Temp: 95°C (ester) = 0.01 7M

Titres are expressed as ml of O.Dl2N NaOH per 10 ml

of reaction mixture o

------------------------------------------------------------

t Titre log(a-x)

------------------------------------------------------------

0 6.70

3600 7.16 o. 781 0 0.204

5400 7.38 0.7664 0.205

7800 7.68 o. 741 9 0.210

9180 7.80 0.7324 0.202

10800 8.00 0.7160 0.207

12600 8.22 006972 0.212

14520 8.42 o.6794 0.21 2

16500 8.64 0.6590 00215

Infinity 1 3.20

4 0

-1 10 !:

1 sec ) (Least Square Method) = 0.216

Duplicate gave = 0.21 6

�------------------------------------�----------------------

99

TABLE 47


Temp: 110° C (ester)= 0.014M

Titres are expressed as ml of O o014N NaOH per 10 ml


------------------------------------------------------------

t Titre log(a-x)

------------------------------------------------------------

0 4.96

1200 5.44 005611

216) 5o80 0.5159

3000 6.06 o.4800

3600 6.24 o.45!3

4200 6.44 o.4216

4800 6.58 0.3979

5580 6.76 o.J655

7500 7.20 0.2742

9300 7.52 O .1931

10800 7.74 0 .12'1$1

11400 7.80 0.1072

Infinity 9.08

4 -1 10 �1 (sec , ) (by Least Square Method)

Duplicate gave

1.03

1.06

1.04

1.03

1.06

1o04

1.03

1.05

1.04

1,04

1 .03

= 1 .04

= 1.03

------------------------------------------------

------------

100

TABLE 48

HYDROLYSIS OF :E,-TOLYLETHYL HYDROGEN SUCCINATE IN WATER



-----------------------------------------------------------


sec

-----------------------------------------------------------

0 5.04

6960 5.92 0.5611 0.311

10200 6.28 0.5159 0.314

12600 6.54, 0.4800 00320

13740 6.60 o.4713 0.308

15120 6.70 o.4664 0.303

18480 7.04 0;4014 0.316

19500 7 .12 0.3874 0.316

20400 7 .18 0.3766 0.315

21900 7.32 0.3502 0.321

Infinity 9-.56 4 ( -1)10 �1 sec (Least Square Method) = 0.319


--------------------------------------------------�---------

101

TABLE 49

HYDROLYSIS OF �-TOLYLETHYL HYDROGEN SUCCINATE IN WATER

Temp: 70°C (ester) = 0.016M

Titres are expressed as ml of OJ)16N NaOH per 10 ml


------------------------------------------------------------


sec

------------------------------------------------------------

0 5.66

1800 6.14 o.6758 0.536

5100 6.90 0.5999 0.532

10800 7.96 o.4654 0.538

12000 8.12 o.4409 0.530

13200 8.32 0.4082 0.540

14700 8.50 0.3766 0.534

15600 8.60 0.3579 0.531

16800 8.72 0.3345 0.531

18000 8.90 0.2967 0.539

Infinity 10.88

1 0 4

!!1 ( S e C -1 ) (Least Square Method)=0.532

DU,plicate gave =0.532

•

------------------------------------------------------------

102

TABLE 50

HYDROLYSIS OF Q-TOLYLETHYL HYDROGEN SUCCINATE IN WATER

Tenp: 73° C (ester) = o.o16M


t Titre log(a-x)

0 4.50

5400 5088 o.4346

6960 6.14 0.3909

7980 6.38 0.3464

9360 6.60 0.3010

11100 6.86 0.2405

12360 7.00 0.2041

13500 7 .14 0.1644

15300 7o34 0.1004

16500 7.44 0�0645

Infinity 8.60

4 -1) 10 �1(sec (Least Square Method) = 0.774


4 ( -1) 10 t1

sec

0.760

0.773

0.770

0.767

0.772

0.762

o. 765

0.771

0.765

-----------------------------------

----------------�--------

103

TABLE 51

HYDROLYSIS OF Q-TOLY�THYL HYDROGEN SUCCINATE IN WATER


Titres are expressed as ml of o.0103N NaOH per 10 ml of reaction mixture.

--------------�--------------------------------------------


-----------------------------------------------------------

0 8.64

900 9.60 0.8195 1 .51

3000 11.42 o.6794 1.53

3600 11.8! o.6415 1.52

4800 12.52 0.5658 1.50

5880 13 .10 o.4914 1.52

6840 13.50 o.4314 1 .51

8700 14.20 0.3010 1.53

9300 1 4.32 0.2742 1.50

9900 14.50 0.2304 1 .51

Infinity 16.20

1 o4�1 (sec-1) (Least Square Method) = 1 .51

Duplicate gave = 1 .51

-----------------------------------�

------------------------

104

TABLE 52

HYDROLYSIS OF p-TOLYLETHYL HYDROGEN SUCCINATE IN WATER

Temp: 85° C (ester )= 0.016M

Titres are expressed as ml of o.o16N NaOH per 10 ml


---------------------------------------------�------------


sec

----------------------------------------------------------

0 5.94

300 6.20 0.5366 2.43

600 6.44 0.5051 2.42

1200 6.90 o.4409 2.50

1500 7 .1 2 o.401 4 2.56

1800 7.28 0.3729 2.50

21 00 7.46 0.3385 2.52

2400 7.64 0.3010 2.56

2700 7.72 0.2833 2.44

3000 7.90 0.2405 2.52

3600 8.20 0.1 584 2.55

Infinity 9.64

4 -1) 10 t1 (sec (Least Square Method) = 2.51

Duplicate gave

-------------------

--------

= 2o52

• ------------

--------------------

105

TABLE 53

HYDROLYSIS OF Q-TOLYLETHYL HYDROGEN SUCCINATE IN WATER

Temp: 90°C (ester)= 0.01 6M

Titres are expressed as ml of O.Q1 6N NaOH per 1 0 ml of reaction mixture.

--------�--------------------------------------------------

t Titre log(a-x)

-----------------------------------------------------------

0 6.54

180 6.78 0.4969 4.09

390 7.02 o.4624 3.93

540 7.20 o.4346 4.02

750 7.46 0.3909· 4.24

1 440 8.04 0.2742 4.07

1680 8.1 8 0.2405 3.96

1950 8.36 0.1 931 3.97

2190 8.52 0.1 461 4.04

2520 s.70 0 .. 0864 4.04

2760 8.80 0.0492 4.oo

Infinity 9.92

1 o4t1

(s ec-1 ) (Least SquarE: Method) O= 4.oo


-----�-----------�------------------�-------------------�--

106

TABLE 54

HYDROLYSIS OF 1(p-ETHYLPHENYLETHYL)HYDROGEN SUCCINATE IN

WATER

Temp: 75° C (ester) = ODl4M

Titres are expressed as ml of 0.01 4N NaOH per 10 ml


�----------------------------------------------------------

t Titre log(a-x) 4 ( -1) 1 0 t

1 sec

-----------------------------------------------------------

0

5400

6600

7800

8400

11700

12600

1 4160

Infinity

4 -1) 10 t1

(sec

5.64

7.34

7.62

7.88

8.00

8.58

8.72

8.92

10.48

(Least

Duplicate gave

o.4969 0.801

o.4564 0.797

o.41 50 0.797

0.3945 0.796

0.2788 0.803

0.2455 0.805

0 .1931 0.800


= 0.807

----------------------------------------�-------------------

107

TABLE 55

HYDROLYSIS OF 1-(12.-ETHYLPHENYLETHYL) HYDROGEN SUCCINATE IN

WATER

Temp: 80°C (ester) = 0.014M


------------------------------------------------------------

t Titres log(a-x) 4 ( -1) 10 �1 sec

-----------------------------------------------------�------

0 5.90

1140 6.58 o.61,2s

4200 7.94 0.4378

5220 8.24 0.3874

8700 9.30 0.1399

10260 9.42 0.1004

11100 9o54 0.0569

12000 9.70 -0.0088

12660 9.80 -0.0555

In:Hrb.ity 10.68

4 -1) 10 t1 (sec (Least Square Method)

Duplicate gave

1 .35

1.34

1 .31

1.37

1 .32

1.32

1.35

1.37

= 1 .35

= 1 .36

----------------------------------�--

-----------------------

TABLE 56

HYDROLYS TS OF 1-(p-ETHYLPHENYLETHYL) HYDROGEN SUCCINATE

IN WATER

108




------------------------�-----------------------------------

t Titre log(a-x)

------------------------------------------------------------

0 7 .14

540 7.54 0.5391 2.03

1140 7.92 o.4ss6 1 .98

1740 8.28 o.4346 2.01

2340 8.60 0.3803 2.03

2940 8.84 0.3345 1.98

3440 9.08 0.2873 1.97

4320 9.34 0.2201 1.95

4740 9.54 0.1644 2.03

7440 '1 0.14 -0.0655 2.02

Infinity 11.00

4 ( -1) 10 t1

sec (Least square Method) = 2.00

Duplicate gave = 2,.01

----------------------------�----�-----------�--------------

109

TABLE 57

HYDROLYSIS OF 1-(E_-ETHYLPHENYLETHYL) HYDROGEN SUCCINATE IN

WATER

Temp: 90° C (ester) = 0.016M


------------------------------------------------------------


------------------------------------------------------------

0

.600

1140

1500

1800

2460

31$0

3420

3840

Infinity 4 -1 ) 1 O t

1 (sec

5.00

5.80

6.40

6.70

6.94

7o44

7.82

7.94

8.12

9.24

(Least

Duplicate gave

0.5366 3.49

0.4533 3.52

o.4o4s 3.41

0.3617 3.41

0.2553 3.48

O .1523 3.44

0.1139 3.46

0.0492 3.47


= 3.44

----------------�--�-----

-------------------------

---------

1 1 0

TABLE 58

HYDROLYSIS OF 1-(E,-METHOXYPHENYL)ETHYL HYDROGEN SUCCINATE

IN WATER

Temp: 20 ° C (ester) = 0.008M

Titres are expressed as ml of 0.01 85N NaOH per 1 0 ml


----------------------------------------------------------

t Titre log(a-x) 4 ( -1) 1 0 t1

sec

----------------------------------------------------------

0 3.74

8700 4.76 0.3222 o.455

1 0500 4.92 0.2878 o.453

11 700 5o02 0.2648 o.452

1 3080 5 .1 4 0.2355 o.456

14700 5.26 0.2041 o.454

16260 5.36 0 .1761 o.451

18600 5.50 0.1 271 o.455

20400 5.62 0.0934 o.453.

21 600 5.70 0.0645 o.458

Infinity 6.86

4 -1)1 O t

1(sec (Least Square Method) = o.457


--�----------�---------------------

-----------------------

111

TABLE 59

HYDROLYSIS OF 1 -(E_-METHOXYPHENYLETHYL) HYDROGEN SUCCINATE

IN WATER

Temp: 28 °C (ester) = 0.018M



-----------------------------------------------------------


sec

-----------------------------------------------------------

0

3000

3600

4500

5400

7020

7800

9120

16200

Infinity

4 -1) 10 !5

1 (sec

6.54

8.-16

8.40

8.70

9.04

9.66

9.80

10.08

11.10

12.04

(Least

Duplicate gave

0.5888 1 .16

0.5611 1 .15

0.5237 1 .11

0.4771 1 .12

0.3766 1 .19

0.3502 1 .15

0.2923 1 .13

-0.0269 1.09

Square Method)• 1 .16

= 1 .16

-----------------�-----------------------------------------

-

112

TABLE 60

HYDROLYSIS OF 1 -(Q-METHOXYPHENYLETHYL) HYDROGEN SUCCINATE

IN WATER


'ritres are expressed as ml of 0.01 85N NaOH per 1 0 ml of reaction mixture.

----------------------------------------------------------

t 11i1t6e log(a-x) 4 ( -1) 10 t1

sec

----------------------------------------------------------

0

1800

2400

3000

3600

3900

4200

5040

6600

7200

7800

Infinity

4 ( -1 ) 10 � sec

. ..

4.16

5.06 0.3181 2.00

5.32 0.2601 2.05

5.54 0.2041 'f;..07

5.70 0-.1 584 2.03

· 5.i6 0.1399 1 .98

5.88 0.1 008 1.98

6.04 0.041 4 1.98

6.38 -0.1192 2.07

6.46 -0.1675 2.05

6.52 -0.2076 2.01

7 .1 4



----------------------------�-�--

-------------�---�---------

113

TABLE 61

HYDROLYSIS OE 1-(Q-METHOXYPHENYL)ETHYL HYDROGEN SUCCINATE

IN WATER

Temp: 40° C (ester) = 0.01.8M

Titres are expressed as ml of O o0185N NaOH per 10 ml


----------------------------------------------------------

t Titre log(a-x)

----------------------------------------------------------

0

420

1020

1260

1800

2220

2520

3030

3300

Infinity 4 -1

)10 �1 (sec

6.14

7.80

7.54

7.80

8.26

8.54

8.74

8.98

9.10

9.98

(Least

Duplicate gave

0.5024 4.49

0.3874 4.45

0.3385 4.49

0,.2355 4.46

0.1584 4.42

0.0934 4.49

0.0000 4.44

-0.0555 4.47


= 4:.4e.

-----------------------------------

------------------------

114

TABLE 62

HYDROLYSIS OF 1-(Q-METHOXYPHENYL)ETHYL HYDROGEN SUCCINATE

IN WATER



of reaction mixture • .

----------------------------------------------------------

t Titre log(a-x) 4 ( -1) 1 O t1

sec

----------------------------------------------------------

0

1038

1110

1272

1 410

1644

1863

2106

2220

Infinity

4 -1) 1 0 t

1(Sec

6.56

1 0.20

10.36

10.68

10.90

1 1.26

11.54

11.80

11.90

12.94

(Least

Duplicate gave

o.4378 8.14

O .4116 8.16

0.3541 8.16

0.3096 8.11

0.2253 8. 1 4

0. 1 461 8.14

0.0569 8.1 8.

0.0170 8.1 7


= 8.18

---------------------------�------------------�

-----------

115

TABLE 63

HYDROLYSIS OF 1-(:12.-FLUROPHENYL)ETHYL HYDROGEN SUCCINATE IN

WATER



------------------------------------------------------------

t Titre log(a-x) 4 ( -1) 10 �1

sec

------------------------------------------------------------

0

5400

7200

9000

10800

12900

15120

16800

18000

20400

21600

Infinity

4 1 10 t1

(sec- )

6.80

7.68 0.7024

7.92 o.6812

8.16 o.6590

8.42 o.6335

8.66 o.6085

8.94 0.5775

9.10 0.5587

9.24 0.5416

9.44 0.5159

9.54 0.5024

12.72

(Least Square -Method)

Duplicate gave

0.297

0.286

0.290

0.296

0.293

0.297

0.299

0.295

0.290

0.288

= 9.291

= 0.290

---------

----------------------------

------------------

----

11 6

TABLE 64

HYDROLYSIS OF 1-(:Q.-FLUOROPHENYL)ETHYL HYDROGEN SUCCINATE

IN WA'J;'ER




---------------------------------------------------------

t Titre log(a-x)

---------------------------------------------------------.

0 6.70

5400 )!I. 96 0.5798 0.531

7260 8.32 0.5366 0.532

9180 8.68 o.4886 0.541

1 0800 8.90 o.4664 0.529

13800 9.36 0.3803 0.541

15000 9.50 0.3541 0.538

16640 9.66 0.3222 0.535

18000 9.80 0.2923 0.544

18900 9.92 0.2648 0.536

Infinity 11.76

1 0 4t1

( S e C -1 ) (Least Square Method) = 0.534


--------------------------------------�-------------------

117

TABLE 65

HYDROLYS 1S OF 1 -(E_-FLUOROPHENYL)ETHYL HYDROGEN SUCCINATE

IN WATER


Titres are express�d �s ml of 0.010N NaOH per 10 ml of reaction mixture.


-----------------------------------------------------------

0 8.56

8100 11.74 0.5289 0.819

9000 11 .96 o.4997 0.812

12000 12.64 0.3945 0.811

12900 12.84 0.3579 0.819

14400 13 .10 0.3054 . 0.818

15600 13.28 0.2648 0.815

17100 13.50 0.2095 0.817

18900 13.70 0.1523 o.817

Infinity 15 .12

1 o4t1

(sec-1) (Least Square Method) = 0.819


--------------

--------------------------------------------

118

TABLE 66

HYDROLYSIS OF 1-(l?_-FLUOROPHENYL)ETHYL HYDROGEN SUCCINATE IN

WATER

Temp: 110 ° C (ester)= 0.016M



-----------------------------------------------------------

t Titre log(a-x)

-----------------------------------------------------------

0 4.92

1200 5.70 o.4564 2.01

1500 5.90 o.4249 2.01

1920 6.14 0.3838 2.13

2200 6.30 0.3541 2.09

3240 6.70 0.2695 2.08

3600 6.86 0.2304 2 .12

4320 7.06 0.1761 2.05

5400 7.36 0.0792 2.06

Infinity 8.56

1 o4t1

(sec -1

) (Least Square Method) = 2.05

Duplicate gave

------�--------------------

= 2.04

,, ---------------------------------·,

119

TABLE 67

HYDROLYSIS OF 1-(£-CHLOROPHENYL)ETHYL HYDRO�EN SUCCINATE IN

WATER


Titres are expressed as ml of 0.007N NaOH p�r 10 ml


-----------------------------------------------------------


sec

-----------------------------------------------------------

0 6.12

3600 6.28 0.7634 0.0755

5400 6.36 0.7574 0.0759

7620 6.46 0.7497 0 .0771

9060 6.52 0.7451 0.0765

11 400 6.62. 0.7372 0.0768

13800 6.72 '

0.7292 0.0768

17100 6.86 0.7177 0.0775

19500 6.96 0.7093 0.0778

Infinity 12.08

1 o4�1

(s@c-1) (Least Square Method) = 0.0782


-------------------------

--------------------------

---------

120

TABLE 68

HYDROLYSIS OF 1-(E_-CHLOROPHENYL)ETHYL HYDROGEN SUCCINATE IN

WATER

Temp: 95° C (ester)= O.OOBM


------------------------------------------------------------

t Titre log(a-x)

------------------------------------------------------------

0 6.14

4200 6.42 0.7528 0.115

5700 6.52 0.7451 0.116

9300 6.76 0.7259 0.118

11280 6.84 0.7193 0.111

12960 6096 0.7093 O .114

16320 7 .18 0.6902 0.118

18360 7.24 o.6848 0.112

20400 7.34 o.67'?8 O .111

22800 7.46 o.6646 0 .111

Infinity 12.08

104t1 (sec-1) (Least Square Method) = 0.113

Duolicate gave = 0.114

--------------

-----�-----------------

-------------

-----------

121

TABLE 69

HYDROLYSIS OF 1-(12.-CHLOROPHENYL)ETHYL HYDROGEN SUCCINATE

IN WATER




-----------------------------------------------------------

t Titre ·1og(a-x)

-----------------------------------------------------------

0 9.08

3420 9.50 o. 9112 0.144

5100 9.70 0.9106 o.144

6600 9.86 0.9020 0.142

7800 10.00 0.8943 0.142

9600 10.22 0.8820 0.145

10500 10.28 0.8786 0.141

12360 10.48 0.8669 0.141

13380 10.60 0.8597 0.142

14400 10.70 0.8537 0.142

Infinity 17.84 4 ( -1) 10 �1 sec (Least Square Method) = 0.142


------------------------------------------------------------

122

TABLE 70

HYDROLYSIS OF 1-(£-CHLOROPHENYL)ETHYL HYDROGEN SUCCINATE

IN WATER

Temp: 1 00° C (ester)= 0.008M

Titres are e;xpressed as ml of o.oo6i NaOH per 1 0 ml


-------�---------------------------------------------------

t Titre log(a-x)

-----------------------------

------------------------------

0 7.30

3660 7.72 0.8062 0. 1 74

5520 7.92 0.7924 0.175

7200 8.10 0.7796 0.1 74

8700 8.24 0.7694 0.171

10980 8.46 o.7$28 0.170

12720 8.62 o.7404 0.170

1 6500 8.98 0.711 0 0.171

1 9500 9.24 o.6884 0.1 72

Infinity 14.12

1 0 4t1

( S e C -1

) (Least Square Method) = 0.1 70

Duplicate gave :;:: 0.1 70

------------------------

--------

-------------

---------------

123

TABLE 71

HYDROLYSIS OF 1-(Q-CHLOROPHENYL)ETHYL HYDROGEN SUCCINATE IN

WATER


Titres are expresses. as ml of 0.0079N NaOH per 10 ml


------------------------------------------------------------

t Titre log(a-x)

------------------------------------------------------------

0

2400

3600

5400

7200

9000

11100

12600

1 4400

18000

21600

5.68

6.14

6.34

6.64

6.94

7.20

7.48

7.68

7.86

8.24

8.60

Infinity 10.84

0.6721

o.6532

0.6232

0 .5911

0.56'1:1,

0.5263

o.4997

o.4742

o.4150·

0.3502

104t1

(sec-1) (Least Square Method)= 0.384


0.387

0.380

0.381

0.389

0.388

0.387

0.389

0.381

0.382

0.386

-----------------------------------------

------------------

124

TABLE 72

HYDROLYSIS OF 1 -(Q-CHLOROPHENYL)ETHYL HYDROGEN SUCCINATE IN

WATER

Temp: 11 5 ° C (ester) =0.008M

Titres are expressed as ml of 0.0082N NaOH per 1 0 ml of

reaction mixture.

------------------------------------------------------------

t Titre log(a-x) 4 ( -1)1 0 t

1 · sec

------------------------------------------------------------

0 4.86

5400 6.04 o.4886 0.600

6300 6.20 o.4654 0.602

7500 6.40 o.4346 0.598

8400 6.52 o.4150 0.591

9000 6.64 0.3945 0.601

9900 6.76 0.3729 0.597

1 0800 6.88 0.3502 0.595

1 1700 7.00 0.3253 0.597

1 2600 7 .1 4 0.2967 0.608

1 3800 7.24 0.2742 0.593

Infinity 9.1 2

1 o4�1 (sec -1) (Least Square Method) = 0.598


---------

----

----------

�---------------

--------------------

125

TABLE 73

HYDROLYSIS OF 1-(:12.-BROMOPHENYL)ETHYL HYDROGEN SUCCINATE IN

WATER




-----------------------------------------------------------

t .. Titre log(a-x) 4 ( -1) 10 �1 sec • -----------------------------------------------------------

0 5.36

15360 6.14 o.6454 0.106

17160 6.22 o.6375 0.106

19440 6.32 o.6274 0.105

21720 6.42 0.6170 0.105

22860 6.46 0.612s 0.104

23760 6.50 0.605s 0.104

Infinity 10.56

1.04�1 (s ec-1) (Least Square Method) = 0.105


----------------------�------------------------------------�

126

TABLE 74

HYDROLY:3IS OF 1-(£-BROMOPHENYL)ETHYL HYDROGEN SUCCINATE IN

WATER

Temp: 100° C (ester)= O.OO�M

Titres are expressed as ml of o.oo4N NaOH per 10 ml


-----------------------------------------------------------

t Titre log(a-x)

-----------------------------------------------------------

0 5.32

5400 5068 o.6s12 0.134

7200 5 • .so 0.6102 o.136

9240 5.92 o.6590 0.134

11040 6.02 o.6493 0.132

13020 6016 o .• 6355 0.136

14460 6.24 0.6274 0.135

16320 6.34 0.6170 0.135

18000 6.42 o.6065 0.135

19860 6.56 0.5933 0.13s

21600 6.62 0.5866 0.134

23220 6.70 o.5775 0.134

Infinity 10.48

4 ( -1)10 �1 sec (Least Square Method) = o.135


----------------------------------

-------------------------

127

TABLE 7§

HYDROLYSIS OF 1-(E_-BROMOPHENYL)ETHYL HYDROGEN SUCCINATE IN

WATER

Temp: 110° C (ester)= 0.004M

Titres are expressed as ml of 0.004N NaOH per 10 ml of

reaction mixture.

------------------------------------------------------------

t Titre log(a-x)

------------------------------------------------------------

0 4.18

3600 4.52 0.5611 0.248

5400 4.66 0.5441 0.238

9000 4.96 0 .5051 0.243

1 0800 . 5 .10 o.4857 0.244

12900 5.24 o.4654 0.240

14400 5.36 o.4472 0.244

16200 5.48 o.42s1 0.244

18000 5.60 o.4082 0.245

19800 5.70 0.3909 0.243

21600 5.82 0.3692 0.246

Infinity 8.16

1 o4t


Dm.plicate gave = 0.244

------------------------------

-----------

---

128

TABLE 76

HYDROLYSIS OF 1-(12.-BROMOPHENYL)ETHYL HYDROGEN SUCCINATE IN

WATER

Temp: 115 °C (ester)= 0.004M



---------------------�-------------------------------------

t Titre log(a-x) 4 ( -1)10 �1 sec

-----------------------------------------------------------

0 3.92

1200 4.06 0.5132 0.351

3120 4.28 o.4829 0.358

4200 4.38 o.4683 0.350

6300 4.60 o.4346 0.354

7500 4.72 · o.4150 0.357

8400 4.80. o.4014 0.356

9780 4.90 0.3838 0.351

11400 5.04' 0.3579 0.351

13080 5 .18 0.3304 0.354

14400 5.28 0.3096 0.355

Infinity 7.32

1 o4�1 (sec-1) (Least Square Method) = 0.354

Dunlicate gave .L

= 0.355

-------------�----------------------------------------------

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EXPERIMENTAL - Shodhgangashodhganga.inflibnet.ac.in/bitstream/10603/74918/7/07_chapter 3.pdf · The esters were decomposed using 10% sodium hydroxide solution. ... culated from the