abstract - kmutt · on-line calculation of plate number and resolution of a chromatograohic column...

On-Line Calculation of Plate Number and Resolution of a Chromatograohic Column

82.

Kan it Krissanangkul*

Abstract

..

GC Plate Program is a Basic Program used in C-R3A data processor.

This program would check temperature and baseline of a gas chromatograph

for readiness prior to sample injection. Plate number resolution and

percentages of- each component in the injected sample were calculated.

Percentages ~aleulated by GC plate program were much closer to the

actual values th·an those calculated by the program provided by the

man uf act urer.

* School of Energy and Materials. King Mongkut 's Institute of Technology

T.honburi •.

•

·• •

•

•

• •

.. ••

•

83

'J

I W " t I

tfqquuLfl;a~tJ1:u1aua (Data Processor> LftLD1lJ11.GTU~Lfl;a'1~ft •

d ~

uu~n (Recorder> iun11uu~nuaq1nn11~iLUl~1fl1lJ1Lfi011W~lJ10iu~n~ •

"' . ... . " fliu'Xlll1ui1'l~wft (Peak> ~1fl1L1a1~: (Retention Time) ua~t1iu11JD..11lJ1ru1aua:

, . ~~

'lla~B-lfltlnm:iu uf1a::ft'1""lulT11lJ1LVIWl'rn'hu11u Mc:Mair ua:: Bonelli <1

> I I tlftl tl <· t

na1111n11Hiu1omu;iftwT1ua~tJ1J.11ru1aHa:na'1a'1fttl1::nau1u1t11J.11lftllfl1J.11ftaLt11a'1 t: '•

1 ·., • vt .:

tl1::J.11auauu uwu1011n11 'lf1Lta::fl1U"XllLD.JU uwu1a (Manual> ft'1UUl ft1iHtl1 ::J.11a ... ..t "' • • "' , ..

ua:alh1l'l~ft11uil:fl10 · 'J'lflL 1'lua::tl11"uwtn4lun111 L fl11::mhJ.11D1811'lult1•n111i1-

llfl1>m1n a~1'1l1nft1J.1Lt1~a'1t11::J.11autru1'1~ufta'1a1"11n~i~1ul;J.1100~1n111Lt111::~ I I 0

t11J.11'dl11LU1fl1J.111ftllfl1J.I L~ULfl1a~tl1:lJ18R81U C-R3A til'1 Shimadzu ' l~tllltl I I t1 I I

LUuti'1au1'1~u~~'1R'l~a1J.111n~~LUU111H1Luanua:t1ia~Lu~1=1~Lflja~~i'11uauuanLMua " . .. , .. .:... ~ .:

q1n1tJ11.1f11).IV11~ , 1un111Lfl11::ltl.l1"1Ul\'!""1~1a"Lfl1a~

l.I I U I '

U~fl11mlLilutJ1::J.11afliS~l~Lft;B\l C-R3A fliU1WL~ul1lrlJLU81 "' <' ...

(Plate number) aiu1~n11Lwn (Resolution) ua:n111Lri11:~tJ1J.11ruWJU " • .., " • d

Area Normalization u:an~:nniiu"\ljjflil1'l~i111ql.1:aur111u~'jf:UJ'llll\l L fl;iN w1e1 .,

1 wnn1 nnnl'lamnu

3.

• 84 ..

• ~ ... u

~11Lml Palmitic Acid 1ID\IU1~l1 BDH (u1::tl1fla~nql:f) LUBlN "' (2) l~U Methyl Ester LftUL~n1~L~U Catalyst

I t: ua::an11auiu~u1ID~t~nL"l.lu

v

II II Ill W f II

~11~'1 (ui"1lli~11) ~a~1nfla1ftui"1!~t1i\lati\ILUa£NLl1L~U Methyl Ester

1 ftUn11vi"1 Transesterif ication 1.ULmnuaaua::~ N~ocH3 LUU Catalyst <2

) II II ~ W

~1a3J1.liu1.~~ft11uLuutru 1.1 un./ua.

• d "' ... ... L fl1£l·UJa unaifl1U11fl011~ 1U GC 9 A ~1aU FID Detector

\ I I I ., ...

'll!l\I Shimadzu flil~'HO'ULfl"ii>~tJ1::u1tun;~ c-R3A, Floppy Disc Drive

... .,, ~ ., FDD- 1 A tla:: Monitor 'q 10\J 1lt"1 L flfJ1nU

~ &I 11 I ~ . . • II

1tl11fltHlWLUl1m.t1ftL'1f'U~1~1'fl0~1~ ) UU. 1.111 3 \Ufl'J 'U"i1~tl1U DEGS 15 °J, d

uu Shimalite 80/100 mesh il"lu1fi1L'qU\~Uundtl1~1 (Carrier gas) I ... • . ... ., ..

!IOll1113Jtltl \I Oven 170 ,,. Injector 180 "l.I. ttn11::au -J UU\1n , " I

a u 1. u ua n Tm ft(it} '1 ..

I • . ., ~111~~\~u1u1Lm1u Basic Lta::r1itf'1 LU~1::'7Ul'1 C-R3A ~t11.u

' t II I f Ill

n111Lft11::l1~~1.n~a11 GC Plate La'lll.J11vi"'tl 30-70 Lilufliu1u~il11u~aua \I

t.i tl &IV ' I 'II

L~a~mtLta::fti~au~1n~1~~::~J.l'Naan>J11.u11u~1uLnaLa;~aun11vii1fl1>J11~tu11u~1uta'll ·v

"' . . ~u11ift 340-370 Lam.J11vi"'tl 90-210 1~un11~11~'1i1Ufl11U~1uU'lltl~Lft1a'1 GC

I ... q cl!! .., v

Li.a::murmm1fl~~rn1v fJ\I L a'lll.J nvift , v • t 1111

2ao-630 ~:: Lifun1111iu1M11'iliu1uL ~fl\1 aiu1~n11 uunt1a~a1H~ii:::fl m1m Tnnru v

tl • • 'II

~ri L ~u 'juua::t1a'lct11 uvia::i11m111 "ctJ.J1 flu1wi La 1~ft'llfl'li1l'l~m::a1mnftiu 1Lilil1U • • tl • ~ ~ tl 'II 'II •

50 "!:: t ilu L 11111Yicl''1'lviL11m1Hliu 1L1M1ft11m 'lllJ'llU flL tl~::mi~ L r:h 1a1via"'1 \I •

., . "' ~1n Peak 'tla'1i1viia:::a1uaamn Lll.11) L iimliu 1(UlLa1~:::11ll'11URfl911JJ Fonnat

•

• ..

•

•

... • •

\

•

• ..

..

•

•• .. •

4 '

85

I II I

l1n1'HUftL1fi1"Lftll.J11~ ... ft 590 ua:: 600 Lfttl'U'J'Jift 660-720 ~tl~Uflin1"~10Lfl;a~ I 11 . 4' I ' I 11 tt' 4'

119!B~n11~:Ytin1111 tl11:'Hi1aa1~9W l\Jvt;a '" n1~:11 fl11:'H9W luan~: 11 ·fl11t'H ' . ., "'

iiaa1.:iL'H"'i1;a\1111 LtlUm.1

N = 25 tr2

w2

LftfJ N

tr = L 1cnt1::

" ... w = fl11"n11.:i~a.:ittfl

( 1 )

Lft~a.:i~1:M1aua C-R3A U1M11nfliu1w1ft~1~~;~flLUULM1ft1l1a;-1u1~ u t II ...

f./'iv .s~} ua::fl1'U·J~~t1a~~rH~ULiJh1'i·t 1a; ~v > ft-3UUfl11illl11.:i'lJ£l.:ittfl ( 'H.I v

• ., • t,, ..,

B1i!L 'Hflllm1U1~ ... 1) \h2111DfllU1WL ft ~a ~ I •

W = 2.A/H

" . . lfttJ A

-41 ..... _cf = l1Ul1ID1U1llLlJU }11v. sec •

H = fl11iJ~~iMu1uLilu }AV ..: ... "' ..: t ... • _cf "" ~ ..: _., .... ...

L 1a1'11t11UUl10LflfJL:ft1a.:iuuID1U1llLlJUU1l1 Lila LUflilULlJU1U1\1 uatll't1Ufl1 w "

aim11 < 1) ~::tft

N =

I

1H» 1 "' ., d

tl1mrfl11n11t~a1m~WlUi1111 14 iia./u1~ ~a~lfl1i11lflLUl1Jfi::1uu11u.:i1uua lfta ~ • • V I '&I • t! *"

~ilfftWlllanaitru1m~-tl fl1L1a1t1: ;u~hi~fl m1i11il.:i'l1£1'1~ft fl11m 'biJ'llU L ttftM ' v

4' '1 I I t

u"'i11ua1 ua:a1u1qn11LWn~1n~fl~1.:i1flt1'1(~aani11nau)~1nn11Y1ilfl1i111fln11~~'MU11 4lj ~ t 'tf ....... d· .II I 4' 4 • v ..: 'Ill

l.l'ft111 qatJuaaiun,flll1aiiii\lln umuaa ( 1ul1 1) u1a"m flfl~::aam.11iutnm.1Y1 s Ltatii v v

tf 4' I &Ill .<f • ., ... tf "' ., ..:

L l'lftlTU ... iJL ua1~.:i~tt1lil.:iraa"'uu~1.11u Luu 3225 '11i1TU 1ID1IiatJ1aJ.1m9191 ( 11u.:i1u'i1H'3 i\Jvt I .,f I 4' 4' I V

i'J iia"9111n111"HamM1Ulavi1li111.JafJu 111 111a11U ... m ua 1t1a'1rraa"w~::afltH ri ... .:i~111111"11

86

t I t .... '1 I

1u~1111'1~ 2. Lijauiti1Lat11u?t1n\I~ 2. UJ.1"\L~uun11\i'i::lftnn\irl'\111J~ 2 f'la a""Yl11 "

...... : .., "t ..... ., .., ... ~101Ii011U L 'Ha'mU.IL lJil1UUfl011U·31UilaOJ.11\1U\1\1tl\ll ft1J.11 L c;llUl'J)J UU1'1J.I

\ " I ~U ' U

ft11>Ja:T11nau1\lll1n \1iL"t\~1Lft11::"t\a1J.111u10\lart11::t1a\ln11l'lilft1J.11lYln11\'l~Y1aa~L1a1 " " ' ., .

1T~1111::n11\111 ri1 J.111 ?t01 ·1\'l-r1u~all11ou::atnH ~nn L ~m iluu;J.11m \111. fl 111a11,::al1fin1-n ' ~ .., .,

'lltl\I flaa"'w"a"\10111tf\I1u ua 1~::iuta\l ltJJ.11nuau L ;tH 1 fl

a1U1~011LW0~11 (Resolution)

Rs ==

., . ' ~ ... ... ... w1 , w2 LlJUfl11J.1n1.1'111a .. nrtfl\1 1 u.a::\1 2

"' ' f.., "' a1u1,n11LWna11uLtlua'1ttU1~nau~ih\1LMUO~fl11~diL;,1u\11'1tl@,J'iiua~n11Lwna11\1;a

f' t f' t .,., t I I

• "i 'l _"f ., _<f ... ... .. ~ .... 1 .......... ... n11l'11 Lfl'UJ1 LYl011l~w L i;m1uJ.1Luan uum L ami1~Mqlt!)11fl£rnWl'1 alua~ uan11::\1tll1~fl111a

u I ti I tt c( tl • 4. -:Ali.: "4 U· f'

iH \111ff11~wm1·11u1\lflH 'tJ.1q1 L1JUil!l'1l11 h.1'11l11::l'lfl\1l'fft\11a L -nal'lum ua 1a'!ari vnm:l1'l , v , t Ill I I 11 II 1 1

~awuuunaan~1nn~1 Yl\l'HJ ft\l L 'llun1HwnL JmHaLat1L 11a1t1a~u'1~1it1111u1tl~ 3 ~a"m1 .. d..,, ..., ..,-'.'!ff' u' •" "'.-.

n111l1a'lla~Lma~1'rl1 ao J.1a./u1\1 L~al'luJ.11ua111a\lflaaw (a1l1'JULJmnatl1a>JJ.1LYlYl) ari ' ' 41.. ... ... ....... "''l"" ....... ..,

a\I rnaa L 'rlfH 11a5 umncH~L?tUL n1 (l'1t1\1 9) ua::u.mmhaaLaYl (l1fll11 o) tNil1J.1110 . ., ' , .,

Lwn~-lnn"u'tYlt1U1\l,1Jru·nu <Rs > 1 > n1111ilmiJ11flnnl'lit1uan11::utr~a11J11n Lu.im111 .. . v .. t 'I '

uaJrnanaan~1nnu1~au1~a~~ru c~~Luu1m.11:a~ftt1a'3n11l'li1fl11J11~n11\'l~) ua~a11J11n " . " " ... ~ ~ ~

aftL1a1na~n111LT111:~a~BU1\lll1nfla nfta~LY1n~1aua~ so • v ' v

, aiu1~n1Hwn'Ylt1'3'111 Ll11a::i·rn.i:'fth1111ua11w1aY1t1vi1Ht1a'31111\11u J TI ~~ L ~u11'1L ~m 1111 . ' ' . ... " ' .

WJna~n~1n1aGLa~"lft~iafla1~iun1ftlt1iu1u11~11 , du ._ "'""'

LL~Oll'3a~Lnu 1 (1.22) UUfta "

" "W1hrn1u1~n11 WJmrntN L Maa 1

•

• •

" •

..

•

•

• ....

• •

•

• •

'• • •

"

87

.. '.. .. ... .. ~ 5. f11 'i1 ~ fl'11 :::'Mll 'UrlQI LDJU Area Normalization 01 'i1 l fl'n :::\11.l'Ulllll 1 flll1 tJ'HU11 lnl

Normalization • .. ... ....

L"aL~HUnu GC Plate Program

1 ~1u Area Normalization fta

P. l

1 Yit.J p. l.

A. l "IT"" x 100

i

.. . .. . .... = u1~1cu1aua:::'lJa'la11lma:::~1 .....

A . = ~u~l YI Peak l

••••••• ( 4)

.. .. GC Plate Program ~::: ll111Wl1-Hru Area Normalization 'lJa'lliliaY1i.l1 .. ..

..: ... ~1 L anum.1fla

.:_· ".: ~ • ..,..: .., ... c: 11.111m1imfia"1nuLfl1a'luu~:::fl1u1rua11~nY11l1aan"1~1nflaaarum.l11n!Jtlu

I I

v11au1'l~na:::a1uaui.ui1~ia:::a1u .. SI t t tJ I

1aua:::~a.:ia11U1la:::i1~fl11.1~1n~LiJu~;'I i.:i11u.:i1u J n. (~1u11.1~ J) Wfl~a'li1l11a:::~1u " al I I I tJ' t"

..... .. _<f .... .. 1 .... ... "I (j • ~:::"l'IUWLuu 92 i ila~a1nnau1.:irnaan111 YJWL1rn.:ith:::Jncu 7 "/o un:::um~wn11fl1u1cuiMfl

\I \I tl I t"I

111::naun1fl1tJ"1JnnYla.:i1ra:::11~1ilu1mrn::: 100 ~ 1 L ilufia.:imJfl1i111ia:::a1uaan ~.i'luctflimli 5 ..

J-7 1 ... ~l ... , aaLa~ J9.8 (PK N09) , a ua1aY1 33.9 ~ (PK NOll) ... ..

J n U'lna1Ha.:inu11u.:i1una.:i Fedeli <5

>

88

1. McNair HM and Bonelli EJ. in "Basic Gas Chromatography" Varian

Instrument 1969, p. 158.

• .>

•

2. Freedman B and Pryde EH in "Vegetable Oil Fuels" Proceeding of •

• the International Conference on Plants and Vegetable Oils as Fuels

1982." American Society of Agricultural Engineers, p. 117-122.

3. Haadad FR, Keating RW and Low GK.C. J. Liquid Chromatography 5.

853 (1982). •

4. McN air HM cmd Bonelli EJ in "Basic Gas Chromatography" Varian

Instrument p. 33. • s. Fedeli E . .:r Aces 60, 404·(1983).

•

••

•

• •

•

•

...

89

GCPLATE PROGRAM

10 REM GO PARAMETERS 20 NEW ~0 PRINT "COLUMN = ?": INPUT B$ 40 PRINT "OPERATOR = ?": INPUT C$ 50 PRINT "TIME TO START CALCULATION?": INPUT TS 60 70 80

PRINT "SAMPLE = ?": INPUT A$ PRINT "FLOW RATE = ? " : INPUT F REM CHECK GO FOR READINESS

90 A1 = LEVEL 100 110 120 130 140 150 160 170 180 190 200 21 0 220 230 240 250 260 270 280 290

WAIT 10 A2 = LEVEL B = ABS(Al -A2) IF 13< 5 THEN 160 PRINT "BASELINE IS NOT STABLE" GOTO 90 T = ABS(CITP#1-CITP#1 M)

IF T<1 THEN 200 PRINT "TEMPERATURE IS NOT STEADY" GOTO 90 PRINT "READY •••• INJECT SAMPLE AND PUSH START BUTTON" ZERO ' REM QUANTITATION AND CALCULATION OF PLATE NUMBER LPRINT LPRINT LPRINT TAB( 20); "DETECTOR RESPONSE" WAIT START WAIT STOP P = MAXPK IF P = 0 THEN 760

300 REM REPORT 310 LPRINT 320 LPRINT "BIOTECHNOLOGY DIV. SCHOOL OF EMERGY AND MATERIALS KMIT T BKK 10140" 330 LPRINT 340 LPRINT "DATE: .. ;DATE$; II TIME: II ;TIME$, "OPERATOR: JI ;C$ 350 L'PRINT "COLUMN: If ;B$, I "SAMPLE: If ;A$ 360 LPRINT "OVEN:- ";CITP#1;" INJECTOR: ";INJT#1, "ATTENUATION: ";ATTE N(FILE); "X10"'II;.DIRG#1 370 LPRINT "FLOW RATE= ";F 380 LPRINT 390 LPRINT 400 R2 = 0 410 W4 = 0 420 A4 "" 0 430 FOR I = 1 TO P 440 A3 = AREA(!) 450 460 470

A4 = A4 + A3 IF RWRT(I) < TS THEN A4 NEXT I

•

0

89-a

480 LPRINT "PKNO" i II TIME" i II AREA";" HEIGHT";" CONC";" ATE NO";" RESN" 490 FOR I = 1 TO P 500 A3 = AREA(I) 510 H1 = HI (I) 520 W3 = A3/H1 530 R1 = RWRT(I) 540 ea = 100*A3/A4 550 IF RWRT(I)<TS THEN ea = 0) 560 ' N:1 = 22500*R1 .. 2/W3"2 570 R4 = 60*(R1-R2)/(W3+W4) 580 IF I = 1 THEN R4 = 0

LPRINT USING 600;I,RWRT(I),A3,H1 ,C8,N1,R4 590 600 610 620 630 640 650 660 670 680 690 700 710 720 730

IMAGE;>### ##.## >######## >#####f ##.## >##### ##.## R2 = R~T(I) , W4 = W3 NEXT I LPRINT LPRINT PRINT uANYMORE SAMPLE ? (Y/N)": INPUT G$ IF G$ = "N" THEN 740 IF G$ = "Y" THEN 700 GOTO 660 PRINT "NEW SAMPLE NAME ? (Y/N)": INPUT F$ IF F $ = uy" 'l'HEN 60 IF F$ = "N" 'l'HEN 70 GOTO 700

740 PRINT II END" 750 END 760 PRINT "NO PEAK" 770 GOTO 90

PL

• -•

• ,a

•

..

. .. •

..

•

• •

•

.. • ..

•

• ... 'i\1'j'l-ll'l 2

I

90

t' t ., I

L l'li:ll1UJJL\Hl1~fliU1Lll1~ GC Plate Program ~Cl ... 9'1'.i101'l1"Ha d

911'1 'l Tlll-1 LUH'ti1l'l1

l I ... l \'ttl\1UlJ L Uil 'J

ti"''i\'j 10111 l1fl I I -1 2 L\ltlil

99 965 969 967

'->J 1 UO<J 1024 1016

85 1043 1097 1070

n 1195 1196 1196

61 1469 1461 1465

44 1901 1887 1894 ·-

34 2290 2295 2292

18 3168 - 3168

14 3225 - 3225

10 3163 - 3163

8 2895 - 2895

5 2192 - 2192

•

• ..

•

•

..

.. •

•

•

..

..

• •

.. ••

•

91

.. ... 91111~\'I 3

' v v v a~m.11~nau1aaa~~a~uiw1i~11

v

Fedeli5

O'Jfli 11W . " ... U1Wfl~

' ..... tJ1aJJ~PJfl 20.2 12-18

... ... i,H ~UJHI 3.7 1-3

1 ...... am:itl 39.8 40-50

aulunatl 33.9 20-42

au1uautl 0.6 0-1

92

DETECTOR RESPONSE

l

10

39 3

4 49

BIOTECHNOLOGY DlY. SCHOOL Or ENERGY AND MATERIALS KMITT BKK 10140

DATE: 001'001'9"8 'TJHE: 91185:38 COLUl1H: 15~ DEGS OVEN: 170 INJECTOR: . 188 rLOU RATE = 14

PKNO TIME AREA HEIGHT 1 1. 92 28212268 1216837 2 23.8 9861 148 3 31. 88 1752 25 4 37 1596 18 5 43.28 246139 . 2101

OPERATOR: KANIT KRISNANGKURA SAMPLE: PALME 5 UL ATTENUATION: 3 X10A 2

CONC PLATE NO RESN e 154 0 3.89 2854 14.59 0.69 4502 3.51 0.63 3888 1.92

94.79 3225 1. 85

•

• •

N N

l °' .. N

°' 0 c.J 0 0

)>

0 w N

•

..

.,

.. •

• •

• ...._

•

• ' • "

' -~

• ..

.. " "• • .. • ~ .,,

..

"'

93

.. ..... ___

8 0 0 0 0 0 0 0 co N Q) .,, N "' ....... •tDld

0 G)

0 ... .,.. .._.. al ;:l -;);; ;:s

~ 0 JC ... co ;);:l

c:: (""

JC ;)~ - s::

c: "«i

0 ·e 1: 3 "7

IO ..... al - 5::1 e ~ - :;: ,,-.,.. (""

c:: ("" .,..

;,S:: (ii "7 ("" -~ :.;.: n II"

... li:i ;);;:t

~ ;:; ("" ~

0 :;::

N

-T~J 0 -

0

0 0 0 0 • 0 -

DETECTOR RESPONSE 94

METHYL PAL111TAT£ 3

9 METH'tL STEARATE ~ z 20 METHYL OLEATE:

12

30

CJtROnATOPAC C-R3A SAMPLE HO 9 REPORT HO 1263

11fl./11U J n

METHYL LINOLEATE

F'1 LE lfETHOD

PKl'IO TI 11E AREA MK IDHO COHC HAl1E

3

4

6

7

10

11

12

e. 3&2

4.382

7. 943

9.717

19.682

11.55

1'L35

12.717

14.511

4869829 4 ho

114& 22.9stb

8291'3 34.6setc·

Ut Y 39.40e

199~.

57.9ue 590 y

26,4SotC 1300 y

31.9sec 2469 y

59 •. hec 15958 y

66.9sec 17.243 161613 y

67 sec 22.483 137529

81.4sec 26. 4.83 2555

72.lsee .... _ .. .,_ ...... _ TOTAL

0.8216

1. 554?

0.8163

9. eu1

8.0112

0.9246,

8.0468

0.2855

2.6971

9,0484

1ee i1B41U' 11

BlOTECHHOLOGY D!V. &CHOOL isr f:NERGY AHD nAr£RIALS KMITT BKK 1

DATE: 86/82/17 TfHEr 1ltl11S~ COLUMNt DEGS 15k ~ . . . . OYEHI 178 lHJttiO~I 188 F'LOll RATE = 19

PKl'IO 1 2 3 4

·s 6 7 8 9

u 11

·12

Tll1£ 8.38 4.3$ 7.94 9.?t!

te.U 11;55 12. 35 12.72' 14.52 17.24 22.48 26.48

AREA 4869828

11.48 821':1 u

861 1.&99 590

13.:'IO 2469

15958 161613 137529

2555

;

H£1GHT t215El48

39 1:!369

u 17 22 41 49

225 2413 1690

35

OPERATOR: KAHIT KRlSHANGKURA $.HPLE• FAME<KIHG> 1 UL ATTtHUATIOHI 2 l<18" 2

COHC a 9.28

U.19 e.u e.2s a.1s 9.32 9.61 3.71

39.79 33.86

0,63

PLATE HO 294 825

1185 1368. 765

430?. 3377 1447 1959 1 ,, 1

1717 3039

RESH 9 a. 92 3.72 1.44 e. 59 9.62 0.82

. 9. 27 Q, 92 1.22 2.12 1. 56

10

r ~

c (J

0 0

(,.)

N

"" ""

• ... ....

•

• •

'

" ...

.. •