sruDY OF THK Nm!I RAPID DKI'ERMINATION METHOD IN QUANTITATIVE ANALYSIS

OF ANIONIC SURFACTANT USINJ SPECI'ROPIDl'OMET.ER

N. HanvaJanawong, N. Ketkaew and v. Wongkittiporn

Department of Chemistry, Faculty of Science,

KMIT Thonburi, Bangkok 10140

ABS:mACT

The aim of this project was to study the New Rapid

Determination in quantitative analysis of linear alkyl benzene

sulfonate <LAS>. The experiment was conducted in order to study the

accuracy and precision of this method, the effect of interferences,

the optimum acid concentrat·ion for extraction and the mole ratio

between LAS and Methyl green in the complex formed. In this method,

the anionic surfactant reacted with Methyl green to form a complex

which would be extracted by chloroform. The absorbance of the complex

in the chloroform layer was measured at wavelength 582 nm. using

spectrophotometer.

The experimental results showed that the accuracy and precision

of this method which were expressed in term of percentage recovery and

standard deviation were 95.48 and 0.0738 respectively. The mole ratio

of LAS and Methyl green to form a complex was 1:1 and the optimum acid

concentration for extracting process was in the range of 0.50-1.0 mole

per dm3• The effects of interferences on the LAS determination were

as follows: phosphate ion and nitrate ion resulted in the positive

error measurement, chloride ion contributed in a positive error when

its concentration was 0.10 mole per liter and up, but non-ionic

surfactant showed no significant effect on the analysis.

In general, the New Rapid Determination method shows some

advantages over the Methylene Blue method <a method which has been

used before> in term of convenience, time-saving and simplicity.

-45-

umh

~ .. .S 0 ~ . ..9 ... ... ' ..l_s ., .. ... ... f.J -:JilmJ21n L 'lJUa \] '11 L Will TV1i"t.Jn 11itmn-.J "B '3R'i.ht:f1 BU'Yllil~ fl a'l'la61U 1 '3$1'3f.J1

~'.'.ltl1ttat:a1t11niiu na~ L ih.AA1at'lu 1-.JGi-:Ji.J111il'.'.l~1 ih 'lml1Lih1t1nt:i1-:J~-:Ja'mhn2121ni.111~ a'11ill"IU 1'3Gi°-:JW1 <surfactant) L iJua'T'l~U't11~ila l\J L 'UGI 1~'11n&1al>l.flufti.ll&11L asSJ U.U-3 flilfl L Duniihl!Pi1-.J "1 ~£1 niihl1ht:'lau '1..11t:"!U1n ttat:niihl~ 111una1-.J L &liir .. hmmJ0n 'l1ta11a~

, 1

U'l'.'.lGi°-:J~'ltl1t:'launiihl branched alkylbenzene sulfonate <BAS> ueii1'1'1W 95% 'llfl-.'l .,, ... ·~ ~ ~ ... ... . ,

f.l-:JifnwEnmalilnmJ1 Lna'11a61U 1 '3lil'3c..J'l'i..11~'16mtl'mi l rnear alky lbenzene su lf onate (LAS) dhuN~'i..l'lt:nfl'lJ [1] a'1mG!tl1MJ'llfl~nl1L'l..l~tlU'l1n BAS i11'li1 LAS LLflU LW'llt:

~ ~

BAS a'a1t1~'l~flUD1'3i11LLat:n11~'3a'.n1Wfle'llf1'3ifu.H-:JWal~Ln~ihM1\Jf1'.JBrl1'3SJlnSJ18LU'lt:U1J u v • u ~ -

ihil~ih L ~tl uat:U1'3~.,~~r11 'l«1 n~rnwn 'lua1u1 TI1 Lttul L u~t L ~8 'llna'1 L Vllil~-:Jmh1~'3 ~ .

-46-

LAS tJina111h::m1tniilvlL~n1 LL611ht:m1001n 26 10111'urni LLat: homolog !ID-lW il-l R... L iiu. linear secondary alky 1 group ~~1U1\~n4m1Ji'3LLlJi 10-14 e::~eu iR~iiun11R11,1~uiu'ln!it11a~LL1-li'lu1u1t:,auilnuLifltt methylene blue il'ILil

, .... .Jq

LAS Li1ua11i1"7un111~ntDJ1~111une-l1tt [2J 1ml1i1u1nnL~11u11 csensitivity> ... .M.. 1 t • •t '1_! I ... .., 'l!J 'l. la' .... LLnt:fl11L 'irnm WU Cse ec lVl y) LJJA21ft6l'Wl LLnt: LD L 1Gl1 LUfl11TIGlnll'\IU1U uen~1muiu

......... ... .... 'l!f • ... ..I • .... I! ....... :s ... ... .., 6 • " ...... 1B8U ~en URR21'3LDLA121'3Uenn-ln1n [394] 6l'1UU'\11U1,tlU~'3U1mUU1t:3'3AL~e"mt11n

i;wji1"7un1-m1tliJJ1tlla'11al'!LL 1~Gl'3u1u1t:,ciutlfW.Ja6i1'3 ~ ~n11ucit:~::611nn111W methy 1 • ...la' ,

blue ~'3,t:L~nn1nu11 New Rapid Determination Method lu1n New Rapid Determination a11a61U1'1~'3U1U1t:~nU,t:Lfl61Li1ua'11u1t:n21u

L n-nfeuTiilinu L unanM'I L ilu.a11Mu1t:~1n.1 ua1T\1n11an111a1~u1t:m1U L n-nt21ufteeinu1 ~1nAae1-nJe4u ,1nilu~~1U1~1~1fl~1616ln~uAltuua'\ILUD1'1~1UB'\IL~1nLA~8"1SLt.IR 1~11~1l;iuLR84 uat:lu~1u1~nA~.Ji LAS·tl~nv1~0 dodecylbenzene sulfonate

1.

2.

3.

4.

.. .. ... d. ii ....... 1RQu•~-~a::neu11111n21"1'11'l'U1,n

~flB1fi1111t:R11U L llun161~ L ~1t:fiU L'Wl11L0613111.h:m 8U L n "1iffiu A113.lft1~~utl;., • ... ..; ::;, !:I .., J 9"_ - • R1n11aGtnauua'3a-lnaGtne'3a11u1t:neuLD'l~Bu ucit:am11~11.1.wa cmole ratio>

, 'B •..., ,! ..lo '}v "" 1t:~11"1a11aGtLL1'1~'3N11l1::,auua:: methyl green nn1L~Ln111a1~u1t:n21u1n-:rit21u , RnB1A11uunM8'3LL"uii1ne"11~ New Rapid Determination

.. . ~mt1Nan21'3a111un1u <interferences) 001"1 "1 ml!Jifln1TV111liwwa11aGtLL1'3~..JU1

1.l1t:,au . , v

L i'.10~1tliu1tlla'11a6lLL'l..Ji..JW1U'lt:~GlUlULLmha1Raf1-:i 'TuinLiMrt New Rapid , Determination

etln.1Tn1ita21"1 , Visible Spectrophotometer uat: pH meter

~fflTnlilaB'11

a11a61LL1'1i'3u11h::,autltlu"11u1'ii'~ tlB dcxiecylbenzene sulfonate il-l , nu1a°UJ1cina1n1nu 458.84 ,

-47-

2530

1. Rmt'lt'l11"tn"iiun0~n76fitmnn#lrlun17afi~a17tJ,-~n0uti-rif0u , U.1a-17a:'.:a1~1.11m1'i:.i1U'tlfl'3a'1i-a(ilLL"Mm'3w1t11:'.:'l«u <LAS> b n1.1nu i.oo 1"1A,. - ,

n11.1c;lflau. ii'1.1. ol1U1u 10. oo «U. ii'1.1. 1.cfluni-1mL~n LL~1 L G11.1n-1(ilitaiJinA11m ili.iihwh~ 1 ::! I I 0 1 q qi t.Jt.J

m~LLm o. 20-3.00 Tuamf!au. (il1J. 'l1u1u 1.00 au. ii'1.1. tbi:U~a'11a:'.:a1~ b1.111an1m tmnu 1

1" LA1"ni'1.1sif1aU. ii'1.1. ol1U1U 13. 00 au. ii'1.1. "lcflun11~ LL~mLlria:'.: 1.u L nrl11.ih n1nULL~h ~ ., "l ' ~ ... "l ' ..I ... 1"'::: a'n(il~1~Aaf!L1"\Jfl1"1.l 2 ¥11"~ 1 a~ 10.00 au.ii'1.1. 1"11.ITIUtlfl'3AaflL1"\Jfl11.ITia'n(il (ilTI~a'e~

A~~ L n1~1~nu LL~1 L ~fl'l1'3~1~ CHCl 3

'lWtli1.11mi- 25 «U. TI1.l. ~1~·t11(il1(iltli1.11mi-~~ L flu

a'17a:'.:a1~ LAS L~1.lmULD1.ltlU 0.40 ~aani'1.1c;leau.~1.1. u11tJ1(il~1n11(il(iln~UA~ULLa'~~1~ I I I 'iJ

LAifl'3a'LtlALmi-1iJ1m~L(llfli nA111.1~11A~u 582 u11ut1.1mi-~ • """ 3 ~ 5]U I 4'1 • """ 2. "mt11'11R11"n11Rm.ITl'i1'11ll7~nBULD'1°IJBULVIR1n17Q~nai&Mauu.a~"1nTl'i1'~ . '

u1a1i-a~a1~ LAS Ltl1.ltlU 1.00 11JLA1ni'1Jc;leau.ii'1J. ol1U1U 20.00 au.ii'1J.

1.aa~ 1.uni-1~unn u~1t9i1Jn1(ilitaiJin~~A111J L il1Jnu 1.uth~~1.i1~1n1i-(il(iln~UA~ULba'~A~~ I ~ V V

<~a'l1nn1i-n(ilae~n 1> ol1u1u 1.00 au.ii'~. 'l1nuun1n11TI(il«B~L~~eu«1ne 1 ~(ilLflu ' a'1i-a~a1~t1B~ LAS Ltl1JtlU 0.80 ~a~ni':JJc;lflaU.(il:JJ. u11tJ1(il~1n11(il(iln~UA~ULba'~~1~

.;, "l "l"l ... ,..,; .. ~' "l 'II b A1"B'3a'L U\'I L(ll'I LW L(111JL (;"ifl'I TIA11:JJ~110.m~r:'3LL(ll 576-590 'U.1 L'U.L :JJ(ll'I

3. n17a71~ni--nb.11~71-..ua1~i'un17iLRi-1~11B"-iwa1i-a~u,-~~~u1tJ7~~au ... , u1a'11a~a1~ LAS A11:JJLtl:JJnuc;l1'3 1 nu TI1n11"TI(ilafl~LrluL~~1n~1ne 2 tl11t1

I I I I I LI I ctl -cSii ~ <ql'lt.J ~ .<Sf Cliil

1(ilA1n11"~(ilnauAaULLa''3 ru A11:JJ~11AaUTIL~n11"(il(ilnauAaULLa''3:JJ1n't1a'(il 'II 'II ,

4. n17Rmt1~~71a1'U~a <mole ratio> 7~~1~a1i-a~u,-~;~u1tJ7~~a111a~ I ,

L man1u mh L;.( L fl~311ll7~n B1J L i-rlf eu q 1.J 1.J -5 9"__ I q q t.J t.J

L m1~:JJa'11«::::a1~ LAS L 'll:JJ'llU 10 w~mflau. (il:JJ. Lta~a'1i-a~a1m :JJ1rnni-m nm1u -5 "i~. ' "lJ "l ... ,., "l~ ::: ... ..I 1~ ..I

10 urnmmm. (il:JJ. L~«~ m111b1m ua1 Lna'11«~a1mNa'fl'3m1:JJtl1:JJ1mi-'t11~u 1 Lunt111~'t1 , 1 ~a':JJnu1.uni-1mt~mL~1n1m1TI(il«e'3m11Ji-hnfl 2

5. n1i-Rfl1t1R11"Tin~e~ua~H111JUsiun1nri~1ff New Rapid Determination • 5.1 Rmt1R111Jlln~B~LU7tltlfl~nlfl4t~n171ilniiuffiw1 <~recovery>

ii • •1.1 tl 1U.1&11mi1 '3·.;i ·1mt:J'll'i:JJ 1H1tli:JJ 1rua'11a(ilbL 1~Gi"w11h~'laU(ll 1:JJn 1i-n(ila ri~

1J I.I 'VI I ' 1

LUtlfl 2 'l1nuu u1U.1&!1flrl1'3UTI't111Utli:JJ1ru LAS n~erltb~1 bm:JJa'1i-a::::a19:JJ1(111"11U LAS 'II ...

..I .,. ..I ' 1 9" "]v .,. ..,; ., ..I ,., n 1 .,. I nn11mh:JJ1rummueua'3 1J L(il~'W~1~1:JJ m1Ji-:JJ1m1L1Ja9Wbtl«~Ufl9't1a'(il Lrn1u1 1J1 L Ai-1~~1 ,

... 0 ' ' 1"'~""' U1:JJ10! LAS brn::::fl1tnruv11b1JE11 L TI1Wlffl1 (ilm:nJAU:JJ1

5. 2 Rmt11111RT11Jusiu~11.u71.JR1 L iln~ L UU1J1~i-"4-..u . ...

tl1a'11«::::a~1~«(ilbb ,-.,,Gi.,,w1tl1:'.:'l«m n:JJnu 1 1" LAi-ni'1Jc;leau. ii':JJ. ol1u1u , ' 10. 00 au. ii':JJ. LaLun11~u~mL~1n1n11"TI(il«fl'3m1:JJ«1nfl 2 a'11a::::a1~a'(ilTI19n1~'l:'.:i1 , ui:JJ1mi- 25. oo au. ii':JJ. u«::::i1A11m n:JJiluTIB'3a'11a::::a19at'ltb 1'3Gi'3w11Ji-~'lam r\1nu o. 40 ,

-48-

"' 1 911,-'NTI

I

LAS 10-6 10-6 M ... Methyl tl1~Tl M green ':l. mole fraction

(ml> <ml> 110'3 LAS

1 0 25 0

2 2 23 8

3 5 20 20

4 7 18 28

5 10 15 40

6 12 13 48

7 13 12 52

8 15 10 60

9 18 7 72

10 20 5 80

11 23 2 92

12 25 0 100

6. M111t1NaDe~a1,-,-111'JUti1~ i Ttil•en1"TM1tf'111'1Qli(1,-a6lu,.~'1ii1~~~at1 , a'1'l'l1.ITT1UihrnumJ1~LLri 1uLGl1TlBB£1U rno3 - ) WBifLWGIBEIEIU (P04 -

3) ua::

RaB1'l~BEIBU <Cl-> ~'3Gl1"Un~BIDEIUL~a1fi~::wuLULL~a'3~1fi'l'l"W1m"Tui8~1 1 1u "Tui8U1 ~ ' ~"' ~ ' u u ~q v v ~ v 0

aaauL~a1unu'l"1WG11~ 1 nw..ia"nua1'la::a18 LAS TI"R11"L11"11UR~Tl ua1n1n17~ae~

LUUL~E1flUDB 2

-49-

.,. ~ ;::t -,.a; <;:: ;::t

'f (Z; c <;:: <;::;i (I-.

r c:: r

-<;::

A

0.180

0.150

0.120

I

"" '.ilhl 1

A

0.170

0 .160

0 .150

I

"" 'HIV! 2 'U

'U

1.0

575 580

-50-

585 . 590 .J

fl11J-IU11flf!U (nm)

I ~

·nJ'VI 3 "

I ~

').06

0. O~- -

0.02 -

0 0.2 .0. 4 0.6 0.8

fl11~L~~~u~a~ LAS(mg/l)

"°' • "°' I o "' q 4' "" u~~~n11~~J~1~1u (Y1a~Y11n11u1uu~~) ~1'Vl1u1Lfl11:'Vl'Vl1u1~1w

~11a~LL1~~~~1u1:~au'luu1~1mh~ 1~u1fi New Rapid Determination ,

1.0

o.s

o.o..._~~~~~~~~~~-'-~~~~~~~~~~~.-.~~

0 0.5 1 • 0 LAS mole fraction

1U'VI 4 "

-51-

. ~ mole fraction ~hn116l61na'l.M'lamLa" ; <A>

'II

8 0.292

20 0.462

28 0.638

40 0.710

48 1.097

52 1.022

60 0.680

72 0.523

80 0.456

92 0.305

fl1't'H~ 3 ~ ff v ... ~ Determination ttit61'3e.Jan11't161aeh1 unTt mt1¥111imnum'3Du'31n New Rapid 'ii

1fiinn1 LAS l.11:1.11fil LAS ... ...

1.li-:1.11n1 LAS fl'3'1-UJGI ... . ~ ..

1.l·n.11n1 LAS nn1 ' ' L 1.lei1 L 'lhP

'lu~1~1mt>Jtl1 .

~

nT'I 16lnau ...... .,. ~v mtom G11m1q1.+~ n111Lf'l'l1t::\ll Gl

.c::ir.. ._. ...,. a

< :1.1ailn1i.i lilu ~ -- .., . < i.iaan'li.i lilu

q ~ ..., •

< i.iaani-i.i lilfl ""' q fV t ...

<i.iaan1JJ Glfl f'IU:l.11

au. Gill. > au. 61J.J. > au. tiliJ. > illJ.l9llJ.) (~)

0.565 0.08 0.645 0.641 95.00

0.565 0.12 0.685 0.680 95.62

0.565 0.16 0.718 0.718 95.83 I I 1v u _.. . ~

t1.ln1t'DUGln11 G1nau¥1U:1.11 (LQaB> 95.48

-52-

~ v LAS L"UllilU

3 <mg/dm >

0.20

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

1 0.370

2 0.445

3 0.478

4 0.400

5 0.522

6 0.312

7 0.355

8 0.284

9 0.355

10 0.415 -x = 0.3936 , S.D. 0.0738

~17'11.lfi1U

Cl 3 <mole/dm >

4.0X10-4

4.0X10 -3

6.0X10-z

8.0X10 -z

1.0X10- 1

1.2x10 -1

2.0X10 -1

3 <mg/dm >

0.19

0.21

0.20

0.19

0.19

0.22

0.31

0.34

-53-

3-P04

3 <mole/dm >

4.0x10 -4

4.0x10 -3

4.0x10-z

1.2x10 -1

2.0X10 -1

3 <mg/dm >

0.19

0.22

0.27

0.33

0.37

0.46

..,: ., LAS L'UIGlU

3 Cmg/dm )

0.20

N03

3 <mole/dm >

4.0x10 -7

4.0x10 -6

4.0x10-5

' "" ' wan111un1UG1un111t~11~~

LAS ~161 LAS ~1~ 3 Cmg/dm ) 3 Cmg/dm )

0.21 0.200 0.203

0.30

0.37

0.53

.... . 7. a1t.lnUG1BU01'l11~au'3 l i:hm1t.liir1ma'1'la1;1u 'l'38i'3W1t.l'l~•mu l~fl1n New Rapid

~ .., q

Determination a1t.1'Ul~'3U q

"' a11a~a1a LAS ~~B l~" 1 au.~"· a11a~a1~ methyl an~~1fl CHC13

2 ~1'3 "' ~~~~~~--1~~~~~~~~~~ "'

u1m1BB1'3 10 au.~"· 0.5 M HZS04 green 13 ~u.~"· A1'3a~ 10 au.~"·

I

tnnu~1n11~~n~u~~mta'3nu .., I ... <!f .J ..i~11J 1~~1n11~~nau L~~~1'3~1u11~n~ ~

'II •

n11~"1G11~1u t~B~1u1ru CJ~~-• ,'II

~auua'3Ti 5a2 c:::Jr---- 1ml1.1i"1m1 2s. o .., .,

inwn:1.1 t illl11UTJB'3 LAS in 1:m "911 au.~" .

-54-

q q ~ ... ' ~ q,q 8. LU18ULnnun'USIBUfl111LR11:::~ LAS LG1n1n New Rapid Determination

.... q,q

nu1n Methylene Blue

1if New Rapid Determination - < "l1f Methylene Blue

1. a11a~&nn LAS 1. a11n:::a1n LAS ... if ... - LG12.1n161 a\.hn ... Wu q - L GIJJ ffW'll1aU •

- Lm2.1a11a:::a1nL2.1naniu - L mm~1·n~::;a1n

l11' L ~83.1'tn6l7fln111'v1 - L mun1G1ita\J1n • - L 002J«°11tlt:n1El

qq

L JJtJtlUUn

a'n6l~1ERnBL-nJBi2J 2 t.I 'll ...

2. ....

2. an6l~1aRaai:iwaiu 2 ....

R1'il R1'il

3. vfj "[I a1'il una'ilRnB -n.Ja1SJ

611na11a::;a1awaa'L~G1

4. t.I i: ' n1B'ilTIUnB'ilRaB 1Wfl12J

~hil.i.aurh .... t.I i: w '

... .... 5. a'nGIGl1El~nB ,. B12J 2 WM

3. .. i."' u' L~B~1'il VWl1U 73J1Gl1 6. .. 1"' q L~B~1'il ~~7uU1SJ1Gl1

t.I i: ' 6l18Raa -n.Ja12.1 .., "[ ' Gl18R&Hl 7~B12J I .

4. .., • 4 41

~fo1~1n1161i;in~u~~La''il 1GIR1n1761GlnnURnUUa''il 7 . • 'II • 'll

,., .. i:Gt1i1""' ' ,., .. i: "[tf[ ... ' 6l18LR7B'ila'L~ 7 W Gl2JLGIBi Gl18LR1fl'ila'L~ 911 Gl2JL!Jlfl1

.. ~ ~ ~ "~'°' I l:! ~ '1u • ~ q I ~•nnT'l L lJ'nl1JL nnum .. rnunB'il1111 L R11::;~ 2 LL1Jtn:t1r;i::;L 'VIU l6l11TJUGIBUn1i1 LRi1~~

TJB'il1n Methylene Blue ~'iln1nift.iif21un11 LnL1a1u1un11 <u1::;2.11fl! 20-30 u1nl I ~ , V

L u21'il~1n~::;4\u'ilu1uilUG1aun1ianGt 2 ~1'3 LLa~GJu'iln1n1,-n1u'36'i'ln

9. aiuNan1i1LR11::;~ LAS l6ln1n New Rapid Determination q .... q,q • 1"' .J

rnnunu'Jn Methylene Blue LLa'Gl'il Gl!Jl12J111111'iln 6

-55-

-" ... ... ... ' . ... ... fl1'l1..:!TI 6 LLit~'3fl1'H U"U.11JL fl!'l..Jt:.Jnfl 171 t lil71t:Vl(;l1'3 "1 !121'3111 New Rap id

Determination nui~ Methylene Blue

r.mn11111n1u "' 3-t UB'3"11fl PO

4

tta::: N03

- iimm

~nfl177'Ufl1U .. l Uf.1'3"11fl Cl

ihrnu

lil11iJU:JlU~1 LVI~ ii,1,m1,1n~1

"' t 11~_,l UWJ1611!1U

in New Rapid Determination

n11~an11111i111:::'1ii~wa1~1u fl1'3111fl <positive error>

. TI1'3'U1flL"f.llil113Jtn3lnUnB'3 Cl

ihrnu ilfi16f'lttGi o. 10 TuaGiei

au. ~3l. iu 1u

95.481.

0.0738

Lnt1a1tJ'l:::3J1m

5 u1n

LBTIH17B1~B..:I

...... 111 Methylene Blue

o '}v <c::i. ' fl1L~~nfl111tlil11t:~

wti1wa1G11un1'3111n

o 'lv --. I TI1L~~nfl111Llil11t:~

W~'Wil1(;11\Jn1'3U1fl

95.05':t

0.0842

Lnt1a1tJ"lt:3l1fU

20-30 u1t1

~ ~ ' ~.., q ~ v .cJ .., 61 1. 11 l TlfUIUt Glu1 L unutLUtutat:'lJ'l'ltnD'"lfUL nlil, fl11U"lt: L 3.lutta:::nei t aumn~ t fl~1flllfl17 LD~'3

~nw21nnil6iB~atJ1:::"la11LutJ7:::tnH1n~, 2527 l1i11 1-14 , 'll q

2. APWA, AWWA and WPCF, standard Methods for the Examination of Water

and Wastewater, 15th ed., APHA Inc., New York, 1981.

3. Yamamoto K. and Motomizu S., Bunseki Kagaku, 1987, 36(5), 335-338 <Japan).

4. Motomizu S., Oshima M. and Kuroda T., Analyst, 1988, 113, 747-753.

-56-