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Chromatography on PapersImpregnated with ZincSilicate: A New Adsorbent forQualitative and QuantitativeSeparation of AminesJ. P. Rawat a , M. Iqbal a & Masood Akhtar Khan aa Department of Chemistry , Aligarh MuslimUniversity , ALIGARII, 202001, INDIAPublished online: 05 Dec 2006.

To cite this article: J. P. Rawat , M. Iqbal & Masood Akhtar Khan (1983)Chromatography on Papers Impregnated with Zinc Silicate: A New Adsorbent forQualitative and Quantitative Separation of Amines, Journal of Liquid Chromatography,6:5, 959-972, DOI: 10.1080/01483918308067018

To link to this article: http://dx.doi.org/10.1080/01483918308067018

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JOURNAL OF LIQUID CHROMATOGRAPHY, 6 ( 5 ) , 959-972 ( 1 9 8 3 )

CBRONATOGWzPIIY OK PAPL‘fS IIIYT3GKATED WITIT Z I N C

SILICATE: A NEW ADSOl‘rl3i”T FOR QUALITATIVL AND

QUk~VTTTATIW3 SEPARATION OF b-PlINCS

J.P.Rawnt, M.Iqb~l anP 3Visoorl A!rhtar Khnn,

Dep? rtiricnt of Chemistry, A 1 ig a rh Mu s 1 i m Un ive I’ s i t y , ALIGARII-202001 ( I N D I A ) .

ABSTRACT

Papers iwpregnpted with zinc s i l i c a t e have been usefl f o r t h e chrotwtogrranhic s t u d i e s of m i n e s taken i n t h e f o m of t h e i r hyc1roclrlorides. R viilries of v c r i o u s amines have been determined ahcl conipared k i t h i t s behcrviour on p l a i n pape r s . Q u e n t i t a t i v e sepPra t ions of dimcthylnmjne from aethplnwine, o( -ncphthyJnmine, o - to lu i ir inc and o-n i t r o w i l i n e ; o-plienyleneiriarrine from m-p 11 e ti y 1 P n e A i am i n e ; il i ph c\ n y 1 a m i l l c f r on1 p i p e r i (7 i n e 11 a ve a l s o been ochieved on colitnms loader? v i t h z h c s i l i c a t e excl-anger.

f

INTROXJCTION

Both papers nna column chromotogr?pphic s t t i f l ies

of amines have been r e p o r t e d by v a r i o u s workers (14).

9 59

Copyright 0 1983 by Marcel Dekker, Inc. 0 148-39 19/83/0605-0959$3.50/0

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960 RAWAT, IQBAL, AND KHAN

It w a s no ted i n t h e s e rnethor?s t h ? t i i n d i s s o c i a t e d m i n e s

h?fl l i t t l e i n t e r a c t i o n wi th t h e s d s o r b c n t s used. IIence

soiiie p r e f e r r e d t o u s e lignnc: escl-nngc c!.roirratogi-apl\y

f o r t h e s e p s r a t i o n of such aivines by v i r t u e of t h e i r

e b i l i t y t o form covp lcxes o f d i f f e r e n t s t o b i l j t y w i t h

t h e loarled m e t a l (5-7). However, i f t h e s a i t s of

aiiiiiies were prerlal-ed, the iou exchange would have

p layed t h e primoi-y r o l e f o r such s e p a r a t i o n s . S ta i in ic

nio1yI)rlate h ? s o n l y been used t o d a t e f o r t he p q c r m t ?

coluitin clirouiatographic s e p r p t i o n s of niiiines w i t h tilis

nret:iocl (8). In oiir p r e s e n t st i i$ies we l invc scpa rP ted

ariine ions token i n the form of t h e i r hy(lrochlor i r1es

on p a p e r s i m p r e p a t e d tvith z i n c s i l i c a t e , an i n o r g a n i c

ion exchrnpe r . 012 t h e l);csis of d i f f e r c i i c e i n E

v r h i c s , solve of t h e r inines hpve PISO been scp?"roted

on columns of z i n c siljccotc exchpnger .

f

Apparatiis: Glass j a r s 20 x 5 CPS ~ 1 1 d 1flistnl:inn KO. 3

p s p e r s t r i p s of 14 x 3 cnrs v e r e used f o r ascc~ndi i iz

cliroirc? togrcoph ic s t rirl j e s . Rergents : Zinc n i t r a t e ( B D V ) , sor3iui:i s i l i c : ! t c (Rieclcl,

Gennnny) i w r c user1 f o r t h e p r e n a r e t i on of i on exclinnge

strins and z i n c s i l i c a t e . A l l o t h e r c l i e n ~ i c a l s used

were o f c n o l y t i c n l g r8de .

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ZINC SILICATE IMPREGNATED PAPERS 961

P r e n s r P t i m of ion exchange pepers : Iniprrpiated

p a p e r s were prepared by dipping t l x s t r i p s (lfiiatmann

No. 3, 1 4 x 3 CIIIS) f i r s t i n a O.IM so l i l t i on of z i n c

n i t r a t e mil r'ere Pllowed t o d ry a t rooin teiaperature

f o r 2 0 minutes. They were then dipped i n a 0.lM

s o l u t i o n of sodium s i l i c a t e f o r about 5 seconds. The

s t r i p s were p l aced o v e r a f i l t e r s h e e t f o r t h e e x c e s s

of t h e r eagen t s o l u t i o n t o d r a j n o f f . These s t r i p s

were completely d r i e d a t room temperature and then

washed twice w i t h d i s t i l l e d wa te r t o remove the excess

of t h e reagent . F i n n l l y they were d r i e d a t room

ten?nerature and used for chromatozraphic s t u d i c s .

-

Preparnt jon of Pinineliydrochlorides: The d r y IfC1 g a s

was f i rs t obtained b y dronwise a d d i t i o n of concen t r a t ed

hydroch lo r i c n c i d i n t o concentrnted sulfi!rjc ?cis. Thc

evolve@ 1ICI ~ P S W P S allor\rerl t o p ~ s s throug!~ t h e antine

so1riti:m i n e t l i r r . 15liiinehyctroclilorirJcs SO ob te incd

were e i t h e r i n s o l i e or l i q u i d form snd werc irninisciblc

w j t t i e t l ~ r r . One F c r c e n t s o l u t i o n of Pni inei~yt~rocl i lor iClcs

were then prennr?d i n water .

De tec to r s : p-Dime ttrylaminobenzcllrlel~y~~e (p-l?i!-IJ) a n d

ninl:y?rin were riser! f o r t h e clctection of va r ious

aminehy4rocl l o r f i l e s . The ninhyrlrin cletector .cc.as

prepa red by d i s s o l v i n p 0.2 gni of niniiydrin i n 100 n i l

of n-butrnol s a t n r a t e d wi th wa te r . p-Dinietliylf vino-

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RAWAT, IQBAL, AND KHAN 962

benzairlehyde d e t e c t o r w a s prevC:red i n etil*>nol + hyProc!i lor ic a c i d wixt i i re token i n t h e r a t i o I? :1 .

NinhyArin T I ' ~ I S u s e 8 t o P e t e c t iiictliyl?rvine, tfiinctiiylaniine,

t r i q e n t y l n m i n c piper i f l ine 8nrJ p-DAB f o r 4- E n i t

B -n 2 p: I t 11 y 1 c 131 i n c_' , o r t 11 o - 3 n 8 pa r a - t o 111 i r7 i n e ; o r t: i o - p'ra- anr' m e t a n i t r o c n i l i n e ; o r t h o - Pntl metr-pLcnylrnc-

flipmine; c~iphcnylcminc; pyr i f i i ne ljenzylniiiine ond

p - a n i s i d i n e .

Procedure: T h e sample s o l u t i o n s were s p o t t e .1 w i t h t h e

h e l p of f i n e c e p j l l a r i e s on t h e ion exchznge p a p e r s .

The s t r i p s were cond i t ionwl in t h e clirotuntogrcpiiic jcirs

contcl ininv t h e s o l v e n t f o r a b o u t 10 rniniites. The

s t r i p s werc t h e n i'ipped i n t h e s o l v e n t t o a l l o w t h e

s o l v e n t t o asccntl t o a d i s t a n c e o f 11 cms i n each c a s e .

-I_

Syn t i i c s i s of z i n c s i l i c a t e : Z inc s i l i c a t e (9) was

prei,;'reci by n i x i n g 0 . l M s o l u t i o n s of z inc n i t r h t e znd

sodiurii s i l i c d t e i n tile voluzie r a t i o 1:l. The w h i t e

g e l a t i n o u s p r e c i p i t a t e so formed was Iwpt s t o n d i n g a t

room temperat i i re f o r 2 4 hoixrs. T h i s was then f i l t e r e d ,

washed and Aried i n an oven a t 40 C . T h e d r i e d p r o d u c t

so ob tn ined was washed aga in w i t h r lcmineral ized w a t e r

and r e t ; t i ned f o r u s e i n column o p e r a t i o n s .

0

S e p a r a t i o n s : For s c p n r a t i o n S t u d i e s a p l o s s coliriin

having a 1ieir:ht of 30 c n anr? d i ame te r 0.69 cni WPS usccl

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ZINC SILICATE IMPREGNATED PAPERS 9 63

in which 2 gm o f z inc s i l i c a t e was taken on i t s g l a s s

wool support . The flow r a t e of t h e e f f l u e n t was

a d j u s t e d a t 5-6 drops/niin. The e l u a t e containing

emine was analysed spec t rophotometr ica l ly (10).

RESULTS AND DISCUSS ION

The adsorp t ion of undissoc ia ted amines on ion

exchanger is n o t p o s s i b l e owing t o t h e i r molecular

s t r u c t u r e s . Two a l t e r n c t i v e WPYS have been suggested

f o r t h e i r s e l e c t i v e r e t e n t i o n and t h e i r subsequent

r e s o l u t i o n in a mixture:

( i) The c a t i o n exchanger i s teken i n a meta) foim

t o enab1.e it t o form complexes of d i f f e r e n t

s t a b i l i t i e s w i t h t h e m i n e s .

(ii) The amines a r e taken i n i o n i c form b y t h e i r

con ve rs ion t o hyrl r o ch l o r i de s . While the former methoc? s u f f e r s from t h e disadvantage

of lack of n i a t e r i ~ l s w h i c h f i r m l y h o l d the metal ion,

t h e l c t t e r i s simple end e a s y t o accomplish. In ou r

prescnt nietiiofl we have chroi:ie togrnplied 17 m i n e -

hyclrochlorides on p q e r s ininregiiated wi. th z inc

s i l i c p t e , a f e i r l y good adsorbent ,

The behzviorrr of d i f f e r e n t ~niinel iyr~roe!~I.ori i les on

papers impregnzted w i t h z i n c s i l i c a t e h a s been s tudied

i n aqueous mil non-aqueous media. The deveI.opers used

were DlifW mt-7 s o l u t i o n s of d i f f e r e n t concent re t ions of

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964 RAWAT, IQBAL, AND KHAN

hydrochlor ic a c i d (O.OO5M, 0.01M and O . l M H C I ) . For

s t .ud ies in nonaqueous mectium, loo$ acetone and acetone + hydrochlor ic a c i d mixture i n the r a t i o 1:l were used.

The Rf v a l u e s obteined a r e shown i n Table I. For the

sake of comparison, R velraes of t h e aminehyrlrochlorides f were a l s o determined on u n t r e a t e d papers i n t h e same

developers . The r e s u l t s a r e presented i n Table 2.

The r e s u l t s of Tables 1 ant1 2 show t h a t on zinc

s i l i c a t e p q e r s aminehydrochlorides a r e s e l e c t i v e l y

absorbed while an u n r e t a r t e d movement o f most of t h e

amines i s observed on t h e p l a i n papers . T h i s implies

t h a t z i n c s i l i c a t e , b e i n g T, good a d s o r b r n t , s e l c c t i v c l y

r e t a i n s c e r t a i n amines (amines w i t h very low R v a l u e s ) .

Zinc s i l i c n t e i s an extremely weak c a t i o n exchanger and

p r e f e r a b l y t a k e s up H+ from t h e s o l u t i o n .

of hydrochlor ic a c i d s o l u t i o n r e s u l t e d in t h e movement

of amine hydrochlor ide s when d i f f ereii t coricent r a t ions of

HC1 were used a s developers .

increase i n concent ra t ion of HC1. Higher concent ra t ions

of HC1 fi irnisl ied g r e a t e r number of H+ i o n s which i n t u r n

displaced t h e amines i n t h e z inc s i l i c a t e l a y e r s . Zinc

s i l i c a t e be ing l e s s s t a b l e i n h igher concent ra t ions of

f

Hence the use

Rf v s l u e s increased with

mineral a c i d s , use of hydrochlor ic a c i d concent ra t ion

h i g h e r than O . l M was avoided.

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N

TB

BIE

- I

3 R

val

ues

of

amin

ehy

dro

chlo

rid

es o

n p

aper

s im

preg

nate

d w

ith

zin

c si

lic

zte

m

ti E ?2 z (1:l)

E

H

r

H

0

M

f

1

1

S1.

A

min

ehyd

roch

lori

de

Itf

vzl

ues

I I

'

I

I

t 8

NO.

Dm

0.005W

O.OlM

O.1M

Ace

tone

A

ceto

ne

+ HC

1

HC 1

HC

1 100%

0.1M

HC

1

1.

2. 3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

13

14.

15.

16.

17.

4 -n

apht

hyla

min

e B-

n a p

h tin

y 1 a m

in e

Pip

erir

lin

e o-

ni t

roan

i li

ne

m

-n i t

roan

il

ine

p-n

i tro

an i

lin

e

0-

to lu

id in

e p-

to

luid

ine

Pyr

ifli

ne

Me t

hy

18 m

ine

Dim

e th

y le

m in

e D

iphe

nyla

m in

e T

rip

enty

lam

in e

o-ph

enyl

ened

iam

ine

m-p

heny

lene

d ia

min

e B

en z

ylam

ine

p-a

nis

idin

e

0.40

0.37

0.80

0.60

0.61

0.51

0.38

0.69

0.75

0.90

0.00

0 .o

o 0.63

0 .o

o 0.52

0.24

0.77

0.46

0.40

0.83

0.50

0.68

0.54

0.46

0.70

0.79

0.92

0.02

0.09

0.69

0.00

0.61

0.26

0.79

0.48

0.46

0.88

0.56

0.72

0.55

0.54

0.73

0.82

0.93

0.04

0.20

0.80

0.00

0.64

0.30

0.81

0.50

0.54

0.90

0.59

0.61

0.60

0.86

0.96

0.40

0.92

0.18

0.70

0.47

0.86

0.75

0.77

0.37

0.95

0.92

0.81

0.90

0.87

T T 0.90

T T

0.0

1

T T 0 .o

T T T

G B

0.91

0.95

0.96

0.90

0.92

0.90

0.91

0.94

0.80

0.69

0.78

0.63

0.86

0.85

0.81

0.89

E

0.78

W m

DMW

= D

emin

eral

ized

wat

er;

T =

Tra

ilin

g f

rom

po

int

of

appli

cati

on

to s

olv

ent

fro

nt.

u

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TABL

d3 - 2

Ri v

alue

s of

am

ineh

ydro

chlo

rid

es o

n p

lain

pa

per

s

t t

S I.

No.

Am

ine h

ycl r

o ck

lo ri

de

Rf v

alu

es

t t

f

DMW

0.0

05

~ HC~ O.

OIM

II

C~

0.10~ II

C~

W

cn a

i. 2. 3.

4.

5.

6.

7.

8.

9.

10.

11.

12

. 13

- 14.

15

. 16-

17.

o( -

nsp

hth

ylam

ine

B-n

Ppli th

y la

lrin

e F

ipe r

i r7 h

e

o-n

i tr

orn

i lin

e

m-n

it r

om i

lin

e

p-n

it ro

mi i

1 i t

ie

o-t

olu

idin

e p-

to l

it i

rl in

e P

yri

c’in

e Ye

ti’y

lrv

ine

D ir

ic t ?

I y 1;. i

n in e

D ip

Ii en y

I P

PI: in

e T

rip

en t-

yl~

riin

e o

-~:~

en

yl

cnc 8

tr

mi

n o

m-n

lieny

l cn

c ~1

inn-

ine

Ben

zplm

jnr

p-m

i s

ir’i

iie

0.5

5

0.5

4

0.8

6

0.6

8

0.73

0.

Go

0.5

8

0.7

8

C.?

2 0

.78

0.

64

0.8

2

0.70

0.60

0.50

0.?

5

0.90

0.6

8

0.5

8

0.9

9

0.7

4

0.7

6

0.7

2

0.6

8

0.8

0

0.8

4

0.S

S

0.G

3 0

.84

0

.?3

0

.63

0

.54

0*70

0.92

0.74

0.7

0

0.?3

0

.79

0

.80

0.

79

0.7

4

0.5

8

0.8

6

0.9

2

0.73

0

.88

0.

77

0.65

0.4

6

0.93

0.59

0.7

8

0.8

2

0.9

6

0.8

8

0.9

5

0.8

6

0.8

3

0.91

0.5

8

0.?8

0.76

0

.92

0.64

D

0.GO

0.94

E 0

.82

5

0.66

H

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TA3J

-E - 3

Sep

prP

tio

ns

Pchi

cveC

1 on

zi

nc

sili

c8

te p

pn

ers

N

c) z

Bin

pry

se

pa

rati

on

s 2 m

So

lvcn

t sy

stem

- O

.OO

5Y H

C1:

( i)

Dim

ethy

lem

ine

(0.0

2)

from

met

hyla

min

e (0

.92

),

6-n

aph

thy

larn

ine

(0.4

61,

B-n

npht

hyl?

niin

e (0.401,

henz

ylP

inin

e (0

.26

1,

uip

erir

lin

e (0.81),

trip

cnty

lam

ine

(0.69),

p-a

nis

idin

e (0.73.).

( ii)

Dip

heny

lam

ine

(0.09) f

rog

a(-

nap

hth

ylm

ine

(0.4

6),

B

-nap

litl

~yl

2min

e (0.40),

$ o

-to

luid

ine

(0.46),

n-t

olu

idin

e (OJO),

o-n

itro

an

ilin

e (0.50),

M

p-n

itro

enil

ine

(0._54),

m-n

itro

anil

ine

(0.681,

py

rirl

ine

(0.791,

E p

iper

idin

e (0.83)

an0

p-n

nis

ifii

ne

(0.7

9).

(iii)

o-ph

enyl

ened

iam

ine

(0.0

0)

from

n-p

hen

yle

ned

iam

ine

(0.6

1).

( iv

) o

-to

luid

ine

(0.46) f

rom

p-t

olu

idin

e (0

.70)

. (

v)

Ben

zyla

min

e (0

.26

from

pip

eri

din

e

(O.4

iO),

py

rid

ine

(0.79) a

nd

uze

tiiy

km

ine

{ 0.92

. T

e ma

ry s

ep

ara

tio

ns

1 S

olv

ent

syst

em -

H20:

( i)

f)im

ethy

lam

iae

(0.00) -

o-t

olu

i?in

e (O

.3@

) -

pip

erif

lin

e (O.@Q).

( ii)

Dim

ethy

lam

ine

(0.00) -

&-n

aph

thy

lam

ine

(0.40) -

met

hy

l~m

ine

(0.9

0).

(iii)

o-pl

ieny

lene

rlia

min

e (0

.0)

- ben

zylp

min

e (0

.24

) -

met

~~

yl:

;rn

it~

e (0.9~).

a 0

-I

Dow

nloa

ded

by [

Uni

vers

ity o

f C

ambr

idge

] at

17:

48 0

8 O

ctob

er 2

014

TABL

E - 4

\o

cn

00

Som

e se

par

atio

ns

on

zin

c s

iltc

ete

col

umns

1 ?

s1.

Sep

arat

ion

s E

Lu

rnts

'V

olum

e 'A

mou

nt of

am

ine-

'

Err

or

NO.

of

hy

dro

chlo

rid

e ef

f lu

sn t

1

(ml)

Loa

ded

Fonn

d.

(Pg

(Pe 1

1. 2.

3.

4.

5.

6.

Me t

hy

lan!

in e

Dim

e th

y 1 am

in

e

4-n

aph

thy

lam

ine

Dim

e thy

1s m

in e

o-t

o l

u id

he

D

ime t

hyla

min

e

o-n

itro

anil

ine

Dim

e th

y la

min

e

m-p

heny

lene

diam

ine

o-ph

enyl

ene

diam

ine

Pip

erid

ine

Dip

hen y

lam

ine

DBW

A

ceto

ne+O

.lOM

E

C1

DW

Ace

tone

+O

. 10M HC1

DMW

Ace

tone

+O.iO

M

HC

l

(1:l

)

(1:i)

(f:l)

(1:l

)

(1:l

)

(1:i

)

DMW

Ace

tone

+O.lO

M HC1

DMW

Ace

tone

+O.lO

M

HC

1

DMW

A

ce to

ne+

O . iO

M HC 1

40

50

50

50

40

50

40

50

40

50

30

40

3600

2600

5000

2600

4100

2600

4 500

2600

4550

4750

2000

40 00

3630

2590

4980

2605

4140

2600

4475

2 590

4500

4730

2000

3960

0.83

0.38

0.40

0.19

0.

97

0.00

0.5

5

0.3

8

z E U

.a m

1.11

0.42

"$ % 2

0,0

0

1.00

tj Ei

DMW

- Dem

iner

aliz

ed w

ater

.

Dow

nloa

ded

by [

Uni

vers

ity o

f C

ambr

idge

] at

17:

48 0

8 O

ctob

er 2

014

ZINC SILICATE IMPREGNATED PAPERS

3000 - I

9 69

- Methy lamine

iDimethylamine

4000

3000 - 9 - 2000

3

E a I000

0

DMW DMW Acetone + 0.1M HCI

a. naphthylamine A.. 0 20 40

Dimethy lamine

!LL 6 0 8 0 100

Volume of effluent (mi)

FIG. 1B Separation of a-Naphthylamine from Dimethylamine.

Separation s o f an ineh yd r o ch 1 or ide s we re t r i e d

on zinc s i l i c a t e papers on the b a s i s of t h e i r behaviour

i n d i f f e r e n t developers used. In some c a s e s the

d i f f e r e n c e s i n R Values were so large t h a t many

ternary separat ions too were p o s s i b l e . The binary and. f

Dow

nloa

ded

by [

Uni

vers

ity o

f C

ambr

idge

] at

17:

48 0

8 O

ctob

er 2

014

970

4000 c-

3000 - 0 - Toluidine

RAWAT, IQBAL, AND KHAN

*

z c

3

E a

FIG. 1C

4000

3 000

- z 2 2000 c

E a 1000

0

DMW -DMW Acetone + 0.1 M HCI r r - -0 - Nitroai

0 20 4 0 6 0 8 0 100 Volume of effluent (mi)

FIG. 1D Separation of 0-Nitroaniline from Dimethylamine.

ternary separations p r a c t i c a l l y achieved are reported

in Table 3.

The separat ions found t o be p o s s i b l e on paper

chromatograms were a l s o t r i e d on columns loaded with

z i n c s i l i c a t e exchanger. The beliaviour of m i n e i o n s

Dow

nloa

ded

by [

Uni

vers

ity o

f C

ambr

idge

] at

17:

48 0

8 O

ctob

er 2

014

Z I N C SILICATE IMPREGNATED PAPERS 971

4000

3000 - - 9 a a

2000 E

I000

0

DMW DMW Acetone+O.lM HCI

*I-- *

rn - phenylene ’ diarnine

0. phenylene diarnine

0 2 0 40 60 80 I00 Volume of effluent (rnl)

FIG. 1E Separation of m-Phenylenediamine from 0-Phenylenediamine.

4000

3 000 c

4 2 2000 c

E 4

I000

0

DMW DMW Acetone+O.lM HCI - r i Diphenylamine

Pi perdi ne

I I

2 0 40 60 80 100 Volume of effluent (rnl)

FIG. 1F Separation of Piperidine from Diphenylamine.

on the impregnated papers r e f l e c t s the exact pattern

of e l u t i o n . 0-phenylenerliamine be ing extremely

adsorpt ive was re ta ined on the column while i ts

m-isomer came out unadsorbed. The adsorbed amine ion

was then e lu ted with acetone + O.1OM HClmixture. The

amine in the e l u a t e w a s determined spectrophotometri-

Dow

nloa

ded

by [

Uni

vers

ity o

f C

ambr

idge

] at

17:

48 0

8 O

ctob

er 2

014

9 72 RAWAT, IQBAL, AND KHAN

c a l l y , The q u a n t i t a t i v e s e p a r a t i o n s p r a c t i c a l l y

a c h i e v e d a r e summarized i n Table 4 and t h e o r d e r of

e l u t i o n and t h e e l u e n t s used a r e shown i n F igu re I.

ACKNOWIJGENENT

Authors a r e t h a n k f u l t o P r o f . W.Rallman,

Chairman, Department of Chemistry, f o r p rov id ing r e s e a r c h

f a c i l - i t i e s . Two of us (M.I.) and (M.A.H.) a r e t h a n k f u l

t o C.S.I.R., Yew D e l h i f o r f i n a n c i a l a s s i s t a n c e .

I. Gaspar i c , J . and Sku t i1 , J . Micro chIm h c t a ,

2. Shimizu , I . J.Chromatogr. 118(1), 96, 1976.

3. W a l 1 , R . A . J.Chromatopr. Go, 195, 1.971. 4. Yoshino,Y. K i n o s h i t a , E . and Sugiyana , Nippon

Kagaku Zassh i , - 86, 405, 1965.

5. Walton,II.F. i n Marinsky,J.A. and Marcus,Y. ( E d i t o r ) , Ion exchange and s o l v e n t e x t r a c t i o n , Marcel De!c!ter, New Y o r k , 4, 121, 1973.

6. Walton,H.F. anf7 N a v r a t i l , J.D. .4nal.Chcni.,

7. Funoseka,?J. Fuj imura,K. and Kuriyaala,S. BunseLi

8. RawPt,J.P. and Singh,J .P . Sep.Sci . , 2 ( 3 ) , 281,

9. Rawat, J .P. anri Iqba 1,V. J. Liq.Chromatogr.,

- 4, 395, 1975. -

- 5, 1975.

Kagaku (Jap.Anal.1 - 39, 104, 1970.

1977.

- 3, 591 (1980) .

10. Sawat ,J .P, end Singh,J .P . Anal.Chem., 2, 738, 1975.

Dow

nloa

ded

by [

Uni

vers

ity o

f C

ambr

idge

] at

17:

48 0

8 O

ctob

er 2

014