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discussions, stats, and author profiles for this publication at: http://www.researchgate.net/publication/233232136

Separation and Quantitation of Anionic, Cationic,

and Nonionic Surfactants by TLC
ARTICLE in JOURNAL OF LIQUID CHROMATOGRAPHY JANUARY 1983
DOI: 10.1080/01483918308066867

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43

2 AUTHORS, INCLUDING:
Daniel W. Armstrong
University of Texas at Arlington
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Retrieved on: 07 December 2015

6(1),
JOURNATOF LTQUTDCHROMATOGR3PHY,

23-33 (1983)

OF
ANDQUANTITATION
SEPARATION
BY TLC
SURFACTANTS
ANIONIC,CATIONICANDNONIONIC
andG.Y. Stine
Armstrong
D.l^J.
of ChemistrY
Department
UniversitY
Georgetown
DC 20057
Washington,
ABSTRACT
T L C i s a p o te n ti a l l y pow erful techni que for the separati on
s
u
rfa c ta n ts . R e v e rs e dphasethi n l ayer chromatograghy(R P TLC )
of
c a n b e u s e d to s e p a ra te e n ti re cl asses of surfactants (i .e.'
a n i o n i c s fro m n o n i o n i c s from cati oni cs). C onversel y' si l i ca ge1
i nydi vi dual ani oni c or cati oni c surfacra' ite
c a n b e u s e d to s e'ps a
im
l a rl
chargedsurfactants. R P TLCcan al so
ta n ts fro m o th e r
b e u s e d to s e p a ra te i n d i v i d ual noni oni c surfactants. U si ng tw o
d .i me n s j o n a fL
l C (w i tn a s p eci al sj l i ca gel pl ate contai ni ng a 2.5
c m s tri p o f re v e i s e d p h a s emateri a' l al ong one gdge) I compl ex
mi x tu re o f s u rfa c ta n ts tv a s fi rst fracti onated i nto cl asses and
th e n (u s i n g th e s e c o n dd i rnensi on)i nto i ndi vi dual components.
S ta n d d rrds i a n n i n g d e n s i to metry w as used for quanti tati on.

I NTRODUCTION
T h e a n a l y s i s o f s u rfa ctants (e.9., detergents' soaps' etc.)
c a n b e a d i ffi c u l t

a n a l y ti cal probl em. S urfactants are general l y

s o m e w h ast o l u b l e i n b o th w ater and organi c sol vents.

They con-

c e n tra te a t i n te rfa c e s a n d tend to bj nd to anythi ng avai l abl e

(l 1 2 ).

T h e re a re a v a ri e ty of spectrometri c, ti tri metri c,

atomi c

a b s o rp ti o n s p e c tro m e tri c and i on-sel ectj ve el ectrode methodsfor

th e a n a l y s .i s o f s u rfa c ta n t s (3-11).

Copyright @ 1983 by Marcel Dekker, lnc.

A l l of these techni ques have

I {023$3.s0/0
l 9/83/060
0 I 48-39

ARMSTROI{G AND STINE

zq

t h e c h a ra c te n i s ti c o f b e i n g sel ecti ve for certai n functi onal

g ro u p s . F o r e x a mp l eb o th t he sodi umdodecyl sul fate el ectrode and
t h e m e th y l e n eb l u e c o m p l e xspectrophotometri cmethodsare sei ect i v e fo r s u rfa c ta n ts w i th sul fate or sul fonate functi onal groups.
for a
C o n s e q u e n tl yth e s e te c h n i q u es gi ve posi ti ve r" esponses
v a ri e ty o f h o mo l o g o u s ,i s o mer^i cand even structural l y di ssi mi l ar
a n i o n i c s u rfa c ta n ts .

An o ther shortcomi ngof these techni ques i s

th a t o n e c l a s s o f s u rfa c ta n ts cannot be effecti vel y anal yzed i n

th e p re s e n c eo f a n o th e r' . The so-cal ' l ed neutral i zati on effect of
(12).
c a ti o n i c w i th a n i o n i c s u rfactants i s w el l documented
re s u l t o f th e s e l i m j ta ti o n s ,

As a

the anal yst has i ncreasi ngl y turned

l c h n i q u es w hi ch pnovi de i nformati on on the

t o p h y s i c o c h e mi c a te
to ta l s u rfa c ta n t c o n te n t i n a sampl e(13) or to chromatography
(1 4 -1 6 ).

Be c a u s emo s t s u rfa ctants are nonvol ati l e w i thout deri -

v a ti z a ti o n , L C o r T L Cm e th o dsare often preferred.

The use of TLC

t o s e p a ra te a m ' i x tu re o f a ni oni c surfactants w as recentl y

d e m o n s tra te d(1 7 ).

In th i s w ork w e not onl y demonstratethe

s e p a ra ti o n o f i d e n ti c a l l y c hargedsurfactants from each other but

a l s o th e T L C s e p a n a ti o n o f t he three maj or cl asses of surfactants
( i .e .,

a n i o n i c , n o n i o n i c a nd cati oni c).

MATER
I ALS
W h a tma n
re v e rs e d p h a s e TLC pl ates (K C 18F),sj l i ca gel pl ates
( K5 F ) a n d h y b ri d M u l ti -K p l ates (C S 5)w ere acti vated at l l 5oC for
bromi de (C TA B ,
t w o h o u rs b e fo re u s e . C e tyl tri methyl ammoni um
Si g m a ), c e ty l p y ri d i n i u m c h l ori de (C P C ,S i gma), cetyl tri methyl -

BY TLC
OF SURFACTANTS
SEPARATION
c h l o ri d e (C T A C ,P f al tz & B auer), dodecyl ami ne(D A '
a mmo n i u m
Al d n i c h ), o c ta d e c y l a m i n e(0A
. , E astman),sodi umdodecyl sul fate
(D B S ,P fal tz & B auer),
(SD S, B i o R a d ), d o d e c y ' l b e n zenesul fonate
s o d i u md i o c ty l s u l fo s u c c i n a t e (S D 0S ,A l dri ch) and sodi uml aurate
( S L , P fa l tz & Ba u e r) w e re r ecrystal l i zed three ti mes from
e th a n o l -w a te r b e fo re u s e . The noni oni c surfactants Tri ton X 100
( T X 1 0 0 , Bi o R a d ), S u rfy n o l 465 (S 465' A i r P roducts) and Igepol
C 0 -5 3 0 (IC 0 -5 3 0 , G A F )w e re used as recei ved. IC 0-530i s
w herethe hydrophi 1i c
n o n y l p h e n o x y p o l y (e th y l e n e oxy)ethanol
p o l y (e th y l e n e o x y )e th a n o l" head-group"averagesfi ve uni ts i n
l e n g th .

S
T X 1 0 0 i s d o d e c y l phenoxypol y(ethyl eneoxy)ethano1.

4 6 5 i s a p o l y (e th y l e n e o x y )ethanol(averagi ng ten uni ts) adduct of

2 ,4 ,7 ,9 -l e l n a m e th y l -5 -d e c yn-4,7-di ol . Gol d l abl e sodi um
t e tra p h e n y l b o ra te (Al d rj c h ) w as used as recei ved. Methanol ,
e th a n o i , me th y l e n ec h l o ri d e and gl aci al aceti c aci d (B aker) w ere
a l s o u s e d a s re c e i v e d .
METHODS
A l l s e p a ra ti o n s w e re d one j n a l 1 3/4 i n. l ong,4
a n d l 0 3 /4 i n . h i g h s e a l e d chromafl exdevel opi ng tank.

i n. w i de
The

p l a te s w e re n o t p re -e q u i l i h r ated w i th sol vent vapor before use.

Se p a ra ti o n o f a n i o n i c s u rfa ctants:

I ut of 0.1 M S D S ' S L' D B S

w a s s p o tte d I c m from the bottom of a 5 x 20 cn si l i ca

a n d S| J O S
g e 1 p l a te .

T h e mo b i l e p h a seconsj sted of 8:1 (v:v) methyl ene

c h l o rj d e :m e th a n o l . T h e a d di ti on of very smal l amountsof acetj c

a c i d to th e mo b i l e p h a s e te n ded to i ncrease the R 1' s but di d not

ARMSTRONGAND STINE

a ffe c t th e re s o l u ti o n .

S p ots w ere vj sual i zed by exposureto 12

v a p o r.
Se p a ra ti o n o f c a ti o n i c s u rfactants:

I yl of 0.i M C P C ,0A , IJA

and CTACor CTABwas spotted 1 cm from the bottom of a 5 x 20 cm

silica

g e 1 p 1 a te . T h e mobi l e phaseconsi sted of 8:1:0.75 (v:v:v)

m e th y l e n e c h l o ri d e :me th a nol:aceti c aci d.

S pots w ere vi sual i zed

b y e x p o s u reto I2 v a p o r.
S e p a ra t' i o no f n o n i o n i c s u r factants:

1 ut of 10%TX 100, IC 0-530

a n d S 4 6 5 rv e res p o tte d o n a 5 x 20 cm reversed phase (C 16) pl ate.

T h e m o b i l e p h a s e c o n s i s te d of 8:2 (v:v) ethanol :2%sodi um
te tra p h e n y l b o ra te (a q ). T he purposeof sodi umtetraphenyl borate
w a s to p re v e n t th e s p o ts fr om streaki ng.

12 vapor w as used for

v i s u a l i z a ti o n .
S e p a ra ti o n o f a n i o n i c , c a t i oni c and noni oni c surfactants:

W h a tma n
C S5 , Mu l ti -K , K C 18F/K sF
20 x 20 crnpl ate w as pred e v e l o p e di n e th a n o l a n d th en acti vated at 115" Cfor 2 hours.
E a c h s u rfa c ta n t mj x tu re w a s spotted (0.5 ur) at a poi nt on the
re v e rs e d p h a s e s tri p .

T h e enti ne 20 x 20 cm pl ate w as then

d e v e l o p e dw i th 7 5 %e th a n o l i n the di necti on of the reversed

p h a s e s tri p .

D e v e l o p m e nwt as stoppedw henthe sol vent front w as

2 c m fro m th e to p o f th e p l ate.

U nderthese condi ti ons, al l

a n i o n i c s u rfa c ta n ts tra v e l at or very nean the sol vent front

(i .e .,

< 2 c m), a l i c a ti o n ic surfactants remai n at or near the

o ri g i n o f th e re v e rs e d p h a se stri p (< 2.5 crn), w hi l e the noni oni c

SEPAMTIONOF SUMACTANTS
BY TLC

r$

27

s u rfa c ta n ts s e p a ra te b e tw e e nthe ani oni cs and cati oni cs.

The 20

fi

x 2 0 c m p l a te i s th e n c u t i n to three separate secti ons i n a

,j

dir e c ti o n p e n p e n d i c u l a rto th e fi rst

r$

rd

devel opment.

T h e fi rs t

c u t s h o u l d b e 2 .5 t o 3 cm bel ow the sol vent front.

This will

i s o l a te th e a n i o n i c surfactants.

be 3 c m a b o v e th e o ri g i n .
t an ts .

T hi s w i l l

The secondcut shoul d

i sol ate the cati oni c surfac-

P e n p e n d i c u l a rs e c o n d arydevel opmentof the pl ates con-

t ai n i n g th e c a ti o n i c a n d a n i oni c sur' factants (aften reacti vati on

of th e p l a te s ) w i l l

g i v e c o mpl ete separati on of these speci es.

T h e mo b i l e p h a s e s fo r s e c o n darydevel opmentare, 8:1 (v:v)

M e C l 2 :Me 0fo
H r th e a n i o n i c s u rfactants and B :1:0.5 (v:v:v)
M e C l 2 :Me 0 H :H OA
fo rc th e c a ti o ni c surfactants.

If one devel ops

t he e n ti re p 1 a te i n th e s e c o n ddi recti on w i thout i sol ati ng the

an i o n i c a n d c a ti o n i c s u rfa c ta nts as i ndi cated, the noni oni c sur" f ac ta n ts te n d to s p re a d a n d c oat the si l i ca ge1 porti on of the
pla te th e re b y o b s c u r' i n ga l 1 o ther components. V i sual i zati on i s
with I2 v a p o r.
Q u a n ti ta ti o n o f s u rfa c ta n ts :

S canni ngdensi tometnyw as done w i th

a S h i ma d z uM o d e l 9 1 0 i n s tru ment. S urfactants coul d be detected

dir e c tl y

i n th e a b s o rb a n c e -r efl ectancemodeat 215 nm. l )etecti on

lim i ts w e n el o w e r w h e nth e d e vel opedpl ate w as exposedto I2

mode).
v ap o r a n d s c a n n e da t 4 0 5 n m (in the absonbance-tnansmi ttance
N DD IS C U S S ION
R ES T J L A
TS
O n e ' s a p p ro a c hto th e T L C separati on of surfactants i n a
m ix tu re i s l a rg e l y c o n tn o l l e d by the changeof the surfactant

ARMSTRONG
AND STINE

h e a d -g ro u p sa s w e l l a s the di versi ty of the sampl e. S i l i ca ge' l

i s a d e q u a tefo r th e s e p a rati on of ani oni c or cati oni c surfactants
fro m o th e r i d e n ti c a l l y c h argedspeci es. N oni oni c surfactants are
b e s t s e p a ra te d b y re v e rsed phaseTLC (R P TLC ). E ven j n R P TLC
n o n i o n j c s u rfa c ta n ts te n d to streak unl ess a " 1i pophi l i c sal t"
s u c h a s s o d i u mte tra p h e n yl borate i s added. Tabl e 1 surnmari zes

TA B LEI
E x p e ri m e n ta lC o ndi ti ons and R 1 V al ues of Indi vi dual l y
S e p a ra te dA n i o n i c, C ati oni c and N oni oni c S urfactants

C o mp o u n d

S tati onary
P hase

MobiI e
P hase

A n io n i c Su rfa c ta n ts
I.
SDS
2. DBS
3. SL
4. SDoS

0.15
0 .09
0.70
4,28

C a ti o n i c Su rfa c ta n ts
1. CTAB
t.

r . I tiu

3.
4.
5.

C PC
DA
0A

0.2r
0.20
0.27
0,42
0.55

N o n i o n i c S u rfa c ta n ts
1. TX 100
2. S 465
3 . IC 0 -5 3 0
a Si l i c a G e l

R1

0.54
0.70
0.45

D C 1 g re versed phase

c 8 :1 (v :v ) M e C l 2 :M e O H

d8,1,0.75 (v:v:v) MeC i 2:MeOH :H 0A c

e 8 :2 (v :v ) Et0 H :2 %s o d ium tetraphenyiborate(6q)

29

SEPAMTION OF SURFACTANTS
BY TLC

andBottom
sections

t:"*:l1r'11]f

-____________f
tie s

SDS
DBS 'fll' '# sDs

NL

{r

r,i#

",$:
u rIl

ig TX100

$l

tco-530
E
o

;;l;crec
;'$
,firb.).,l}

lt

CpC

DA
!i,:!FliJ

OA
clF;+

KCl8F

F i g u re 1 : S c h e ma ti co f a tw o dj mensi onalTLCseparati on of
e l e v e n s u rfa c tants on a composi t reversed phasesilica

g e 1 p 1 a te. The fi rst

devel opment(on the

re v e rs e d p h a s e stri p) separatedthe surfactants

a c c o rd i n g to c l ass.

devel opmentof the top

S econdany

a n d b o tto m s e c ti ons of the pl ate r" esul ts i n compl ete

s e p a ra ti o n o f j ndi vi dual sunfactants. S D S= sodi um
d o d e c y sl u l fa te , D B S= dodecylbenzenesul
fonate, N L =
s o d i u m l a u ra te , S 465 = S urfynol 465, TX 100 = Tri ton
X1 0 0 , IC 0 -5 3 0= Igepol C 0-530,C TA C= cetyl tri rnethyI a mmo n
u im c h l o r i de, C P C= cetyl pyri di n i um chl ori de,
D A = d o d e c y l a m i ne,0A = octadecyl ami ne.

30

ARMSTRONGAND STINE

th e s e p a ra ti o n c o n d j ti o n s for each c' l ass of surfactants.

R r' s o f th e c a ti o n i c s u n factants can be al tered (i .e.,

The

i ncreased)

c o n s i d e r" a b l yw i th a s l i g h t i ncrease i n the concentr^ati onof aceti c

a c i d i n th e mo b il e p h ase. The separati on of surfactants w i th

' i d e n ti c a l h y d ro p h y l i c h e a d gnoups(i .e.,

D A and 0A or Tx 100 and

IC 0 -5 3 0 ) i s d e p e n d e n to n the si ze of the hydrophobi c" taj l " .

G e n e n a l l y th e l a rg e r th e hydrophobi cporti on of the sunfactant,
th e g re a te r th e R 1 .
T h e a n a l y s i s o f s o l u t i ons contaj ni ng sunfactants of di ffe re n t c h a r^ g ec a n b e a d i ffi cul t

pr^ocessbecauseof preci pi tati on

a n d " n e u tra l i z a ti o n " e ffe cts (12).

R P TLChow
,
ever,can be used

to s e p a n a tes u n fa c ta n ts b y cl ass (see Fi gure 1).

A 75%ethanoi

mo b i l e p h a s e te n d s to c a n n y ani oni c sunfactants w i th the sol vent

fro n t a n d l e a v e c a ti o n i c surfactants near the oni gi n.

P erpen-

of pl ate secti ons near the sol vent

d i c u l a r s e c o n d a ryd e v e l o prnent
fro n t a n d o n i g i n w il l th e n sepanatethe anioni c and cati oni c sur' fa c ta n ts i n to i n d i v i d u a l compounds.The secondanydevel opment
c a n n i e s th d s u rfa c ta n ts fro m the reversed phase stl i p
silica

i nto the

g e l p o rti o n o f th e pl ate w henefnacti onati on occuns

(F i g u n e 1 ).

Se c o n d a ryd e v el opmentof the w hol e TLC pl ate or the

s e c tj o n o f p l a te c o n ta i n i ng the noni oni c surfactants produced

i n d i s ti n g u is h a b le s m e a rsoven muchof the p1ate.
Q u a n ti ta ti o n o f s u r" fa ctantsby scanni ngdensi tometry i s a
re l a ti v e l y

s tra i g h t fo rw a r" dpnocess. It i s possi bl e to di nectl y

s c a n u n tre a te d s p o ts a t w avel engthsfrom 200 to 215 nm. S ens i ti v i ty

a n d s e l e c ti v i ty

c an be enhancedb.y usi ng a vani ety of

SEPARATIONOF SURFACTANTS
BY TLC

3t

N
c
@'

964
I

6
o

4812
CTACAmount,llg
Figur e 2:

Calibr at ion

pl o t

of peak area vensus arnount of the

s t andar d s unf a c t a n t

(CTAC) chromatographed.

The

' ins ent s hows t h e a c t u a l p e a k s

obtained from scanning
dens it om et er y

(at 405 nm).

v i s u a l i z a ti o n o n c h a rri n g techni ques (17, 1g).

Fi gure 2 show sa

s c a n o f fo u r G T A Cs ta n d a rds (r = 405 nm aften vi sual i zati on w i th

I2

v a p o r) a n d th e c o rre s pondi ngcal i brat.i on curve.

It i s a p p a r" e n tfro m th e l .i terature that exhausti ve chroma_

to g ra p h i c s e p a ra ti o n s a re p r" esenti ythe most effecti ve meansof

a n a l y z i n g c o mp l e xs u rfa c ta nt mi xtur" es. TLC i s show nto be a
h i g h l y e ffi c i e n t

a n d i n e x pensi vetechn.i quefor the anal ysi s of a

v a ri e ty o f s u rfa c ta n t a n d surfactant mi xtures.

32

ARMSTRONG
AND STINE

ACKN()l,lLEDGEMENT
T h i s w o rk w a s s u p p orted by grants from the N ati onal S ci ence
F o u n d a ti o n (C H E-8 1 1 9 0 55)
and W hatman
C hemi calS eparati on
D i v i s i o n , In c .

Weg ra te ful l y acknow l edge

thei r assi stance.

R EFE R E N
ESC
l.

F e n d l e r, J .H . a n d Fendl er, E .J., C atal ysi s i n Mi cel l ar and

M a c ro mo l e c u l a rS y stems,A cademi cP ress, N ewY ork, 1975.

2.

R o s e n , M.J ., S u rfa c tants and Interfaci al P henomena,

John
t,| i l e y & S o n s , N e wYork, 1978.
| ^ l a n g ,L .K . a n d L a n gl ey, D .F., N . E ngl . W ater^W onksA ssoc.,
8 9 , 3 0 1 (1 9 7 5 ).

4.

Wa n g ,L .K. a n d R o ss, R .G., Int. J. E nvi ron. A nal . C hem.,4,

2 8 5 (1 9 7 6 ).

5.

H i g u c h i , K., S h j moi shi , Y ., l ' fi yata, H ., Toei , K . and Y ayami ,

T ., A n a l y s t, 1 0 5 , 768 (1980).

6.

W a n g ,1 .K ., J . A m . 0i l C hern.S 0c.,52,339

7.

V y tra s , K., D a j k o v a , M. and Mach,V ., A na1. C hi m. A cta, I27,

1 6 5 (1 9 8 1 ) (a n d re fe rences therei n).

8.

C ri s p , P.T ., E c k e rt , J.M., Gi bson, N .A ., K i nkbri ght, G.F.

a n d We s t, T .S ., A n a 1. C hi m. A cta, 87, 97 (1976).

9.

L e b i h a m,A. a n d C o u rtot-C oupeJ,J., A na1. Lett.,

10.

K i rc h , B .J . a n d C l arke, D .E ., A nal . C hi m. A cta,67,387

11.

R e n d a l l , H .M., J . C hem.S oc. FaradayTrans., 72, 48L (1976).

12.

W a n g ,L .K . a n d L a n g l ey, D .F., N . E ngl . W ater tJorks A ssoc.,

9 0 , 3 5 4 (1 9 7 6 ).

(1975).

10, 759 (1977).

(1973).

13. A rm s tro n g , D .W ., L afranchi se, F. and Y oung, D ., A na1. C hi m.

A c ta , 1 3 5, 1 6 5 ( 1 9 8 2).

14. S u l l i v a n , W .T . a n d S w i sher, R .D ., E nvi ron. S ci . Technol . 3,

4 Bl ( l e 6 e ) .

S E P AM T ION OF SURF ACT ANT S]]Y TLC

33

15 .

H u b e r, J .F .K., K o l d e r, F.F.l ' 4.and Mi 11er' ,J.M., A nal . C hem.,

4 , l o s (1 9 7 2 ).

16.

1" 1.,A nal. C hem.,52, 2275

N a k a e , A., T s u j i , K. a n d Y amanaka,
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