Experiment 1 QUALITATIVE ANALYSIS of ORGANIC COMPOUNDS

A. intro !"tion T#e $n$%&'i' $n i entifi"$tion of !n(no)n or*$ni" "ompo!n ' "on'tit!te' $ +er& import$nt $'pe"t of experiment$% or*$ni" "#emi'tr&. T#ere i' no efinite 'et pro"e !re t#$t "$n ,e- *ener$%%& $pp%ie to or*$ni" .!$%it$ti+e $n$%&'i'. V$rio!' ,oo(' #$+e ifferent $ppeoe"#e'/ ,!t $ '&'tem$ti" $ppro$"# ,$'e on t#e '"#eme *i+en ,e%o) )i%% *i+e *oo re'!%t'. 0efore o!t%inin* t#e *ener$% '"#eme/ one or t)o point' of pr$"ti"$% import$n"e '#o!% ,e 1ot2o 3 Q!$ntitie' of '!,'t$n"e for te't'. 4or mo't te't' $,o!t 5/1 * 'o%i or 5/1-5/1 mL 61-7 rop'8 of %i.!i m$teri$% 6NOT MORE8 '#o!% ,e !'e . 9. Re$*ent' %i(e%& to ,e met )it#in or*$ni" $n$%&'i' $re on t#e re$*ent . '#e%+e'. St! ent' $re $"i+i'ei to e+e%op $ *ener$% (no)%e *e of t#e p#&'i"$% "#$r$"teri'ti"' of "ommon or*$ni" "ompo!n '. If in o!,t $,o!t t#e expe"te re'!%t of $ te't ,et)een $ "ert$in "ompo!n $n $ re$*ent/ "$rr& o!t $ tri$% te't )it# $ (no)n "ompo!n $n "omp$re )it# t#e !n(no)n. " Q!$ntitie' of '!,'t$n"e eri+$ti+e'. St! ent' #$+e )$'te m!"# time $n m$teri$% in t#e p$'t ,& t$(in* too %$r*e $ .!$ntit& of '!,'t$n"e for prep$r$tion of $ eri+$ti+e. In *ener$%/ QS-1 * 6or 5.: - 1 mL8 of '!,'t$n"e *i+e' t#e mo't '$ti'f$"tor& re'!%t'. If $ pr$"ti"$%. ,oo( in'tr!"t' one to !'e %$r*er .!$ntitie' 67-; * or more), the .!$ntitie' '#o!% ,e '"$%e o)n to 1 * or 1 mL of t#e !t ino)n '!,'t$n"e $n "orre'pon in* .!$ntitie' of re$*ent' '#o!% ,e !'e . Gener$% S"#eme of Ao$%&'i' <

L Pre%imin$r& Te't'/ 6$8. Note p#&'i"$% "#$r$"teri'ti"' - 'o%i / %i.!i / "o%o!r $n o o!r/ 6,8. Perform $n i*nition te't 6#e$t 'm$%% $mo!nt on met$% 'p$t!%$8 to etermine )#et#er t#e "ompo!n i' $%ip#$ti" or $rom$ti" 6Le. %!mino!' =$me - $%ip#$ti"> 'oot& f%$me $rom$ti"8.

?. P#&'i"$% Con't$nt'/ Determine t#e ,oi%in* point or me%tin* point. Di'ti%%$tion i' re"ommen e in t#e "$'e of %i.!i ' 6'ee Appen ix 78. It 'er+e' t#e !$% p!rpo'e of eterminin* t#e ,.p./ $' )e%% $' p!rifi"$tion of t#e %i.!i for '!,'e.!ent te't'. @ 7. An$%&'i' for e%ement' pre'ent/ At CIO %e+e%/ t#e e%ement' pre'ent )i%% ,e to% to &o!/ ,!t re$ !p t#e met#o .

I So%!,i%it& te't'
T#e 'o%!,i%it& of t#e !n(no)n in t#e fo%%o)in* re$*ent' pro+i e' +er& !'ef!% iQf$m$tion. In *ener$%/ $,o!t 7 mL of t#e 'o%+ent i' !'e )it# 5/1 * or 5/1 mL 61-7 rop'8 of Ae '!,'t$n"e. T#e "%$'' of "ompo!n m$& ,e in i"$te from t#e fo%%o)in* t$,%eB 4rom t#e pre+io!' te't' it i' often po''i,%e to e !"e t#e f!n"tion$% *ro!p' pre'ent in me !n(no)n "ompo!n . Con'!%t ix. 'peetxC$ )#en $+$i%$,%e. In i+i !$% te't' $re t#en p$ forme to i entif& $n "onfirm t#e f!n"tion$% *ro!p' pre'ent.
Note :

SOLU0ILITY TA0LE
GROUP OF COMPOUNDS Lower members of series. Neutral, e.g. ak.o ols! "#i$i#, e.g. a#i$s, % e&ols! 'asi#, e.g. ami&es Most ami&es (e)#e%t *++ ami&es wit o& aromati# ,rou&s Most a#i$s, most % e&ols. Most #arbo)-li# a#i$s. .-$ro#arbo&s, &itro -$ro/#arbo&s, alk-l or ar-l ali$es, esters a&$ et ers. .ig er mofe#ularweig t al#o ols, al$e -$es a&$ keto&es

Gro!p C%$''ifi"$tion . Te't'

1 Students are strongly advised against carrying out . unnecessary tests, since not only are they a waste of time but also increase the pna{ibiHty of error. A us it is pomdess to first test for alcohol or ketone in a basic compound containing nimi ggen! "nstead tests for amines, etc. should be $o&e on such a compound. 0 " s-stemati# approach cartnot be overemphasised in . group classification tes#s 1b avoid confusion and error

No +

R1"G1N2 "ND 21S2

CL"SS

0 8 9

Soluble i& #ol$ or ot water. Neutral, a#i$i# or 34f tbe u&k&ow& is soluble $o basi#. 32est wit NOT perform solubility tests f5itr&us or be6.,7 i&uiCStoi/ %a%er7 Soluble i& $il. HGI 'asi# Soluble i& $il. NaO. "#i$i# Soluble i& Na.C:8 Stro&gl- a#i$i#

S 4&soluble i& water, a#i$ a&$ all#ai 2

Neutral

Con'!%t$tion of Liter$t!re On"e t#e f!n"tion$% *ro!p #$' ,een i entifie / referen"e i' m$ e to t$,%e' in $ ,oo( on or*$ni" $n$%&'i'/ for $''e''in* po''i,i%itie' $n for t#e prep$r$tion of '!it$,%e 'o%i eri+$ti+e'. It '#o!% ,e note t#$t )#i%'t t)o '!,'t$n"e' )it# t#e '$me f!n"tion$% *ro!p may 'ometime' #$+e +er& 'imi%$r ,.p. or imp./ 'o%i eri+$ti+e' "$n !'!$%%& ,e "#o'en from t#e %iter$t!re/ )it# m.p. ifferen"e' of $,o!t 15 6or more8/ )#i"# i'tin*!i'# ,et)een t#e t)o po''i,i%itie'/ e$ample% f Prep$r$tion of eri+$ti+e' T#e fin$% "#$r$"teri'$tion of t#e !n(no)n i' m$ e ,& t#e prep$r$tion of '!it$,%e 'o%i eri+$ti+e'. T#e eri+$ti+e '#o!% ,e "$ref!%%& 'e%e"te $n it' m.p. '#o!% prefer$,%& ,e ,et)een D5 - 1:5 for e$'e of "r&'t$%%i'$tion $n m.p. etermin$tion. Prep$r$tion of one eri+$ti+e '#o!% ,e $ttempte . T#e eri+$ti+e '#o!% ,e p!rifie ,& re"r&'t$%%i'$tion/ rie $n t#e m.p. etermine . Deri+$ti+e' '#o!% ,e '!,mitte "orre"t%& %$,e%%e for $''e''ment to*et#er )it# t#e re"or . 0. Q!$%it$ti+e An$%&'i' for E%ement' in or*$ni" -"ompo!n ' t#e e%ement' "ommon%& o""!rrin* $%on* )it# "$r,on $n #& ro*en/ $re ox&*en/ nitro*en/ '!%p#!r/ "#%orine/ ,romine $n io ine. T#e ete"tion of t#e'e ement' epen ' !pon "on+ertin* t#em to )$ter-'o%!,%e ioni" "ompo!n ' $n t#e $pp%i"$tion of 'pe"ifi" te't'. T#e ete"tion of +$rio!' e%ement' pre'ent in $n or*$ni" "ompo!n i' "$%%e .!$%it$ti+e $n$%&'i'. C$r,on $n #& ro*en $re pre'ent in $%mo't $%% t#e or*$ni" "ompo!n '. Ot#er "ommon%& pre'ent e%ement' in or*$ni" "ompo!n ' $re ox&*en/ nitro*en/ #$%o*en'/ '!%p#!r $n 'ometime' p#o'p#or!'. i. Dete"tion of C$r,on $n E& ro*en. C$r,on $n #& ro*en $re ete"te ,& #e$tin* t#e or*$ni" "ompo!n )it# "!pri" oxi e 6C!O8 'tron*%&/ )#ere "$r,on i' oxi i3e to "$r,on ioxi e $n #& ro*en to )$ter. C$r,on ioxi e i' te'te ,& %ime )$ter te't/ )#ere$' )$ter i' te'te ,& $n#& ro!' "opper '!%p#$te te't.

An re$"tion' i' B C + 2Cu0

CO + 2Cu

M t e #om%ou&$

2H + Cu0
4& Me #om%ou&$

DO

H20 + Cu CaC03 + H20

C02 + Ca(OH)8
"ble water mr#- . .

5H20 + CuS04 ~ CuS04. 5Hz0 a& -$rous T#e *i+en or*$ni" "ompo!n i' mixe )it#- r& "opper oxi e 6C!58 $n #e$te in $ #$r *%$'' t!,e. T#e pro !"t' of t#e re$"tion $re p$''e o+er 6)#ite8 $n#& ro!' "opper '!%p#$te $n t#en ,!,,%e t#ro!*# %ime )$ter. If "opper '!%p#$te t!rn' ,%!e !e to t#e form$tion of C!S5;.:E15 6,& )$ter +$por8 t ;#en t#e "ompo!n "ont$in' #& ro*en. If %ime )$ter i' t!rne mi%(& ,& C5 1/ t#en t#e "ompo!n "ont$in' "$r,on. 1- Dete"tion of Nitro*en/ S!%p#!r $n E$%o*en'. E%ement' %i(e nitro*en/ '!%p#!r $n #$%o*en' $re ,on e "o+$%ent%& in t#e or*$ni" "ompo!n '. In or er to ete"t t#em/ t#e'e #$+e to ,e "on+erte into t#eir ioni" form'. T#i' i' one ,& f!'in* t#e or*$ni" "ompo!n )it# 'o i!m met$%. T#e ioni" "ompo!n ' forme )i$* t#e f!'ion $re extr$"te in $.!eo!' 'o%!tion/ $n "$n ,e ete"te ,& 'imp%e "#emi"$% ft'i'. T#e $.!eo!' 'o%!tion o,t$ine ,& extr$"tin* t#e f!'e m$'' in )$ter i' "$%%e 'o i!m c&fta or 'assaigne(s extr$"t. Prep$r$tion of 'assaigrre(s )$tract 6or So i!m Extr$"t8 ,& A 'm$%% pie"e of 'o i!m i' #e e *ent%& in $n i*nition t!,e ti%% t#e 'o i!m me%t'. A,o!t :5 to 95 m* of t#e or*$ni" "ompo!n i' $ e to t#i' $n t#e t!,e #e$te 'tron*%& for 1-7 min!te' to f!'e t#e m$teri$% in'i e it. After "oo%in*/ t#e t!,e i' "$ref!%%& ,ro(en in $ "#in$ i'# "ont$inin* $,o!t 15 to 75 mL of i'ti%%e )$ter. T#e f!'e m$teri$% $%on* )it# t#e pie"e' of i*nition t!,e i' "r!'#e )it# t#e #e%p of $ *%$'' ro $n t#e "ontent' of t#e "#in$ i'# $re ,oi%e for $ fe) min!te'. T#e 'o i!m '$%t' forme in t#e $,o+e re$"tion' (Le NaCN, Nal/S/ N$F or N$SCNG i''o%+e. Ex"e'' of 'o i!m re$"t' )it# )$ter to *i+e 'o i!m #& roxi e. T#i' $%($%ine 'o%!tion i' "$%%e I$''$i*ne@' extr$"t or 'o i!m extr$"t. T#e 'o%!tion i' t#en fi%tere to remo+e t#e in'o%!,%e m$teri$%' $n t#e fi%tr$te i' !'e for m$(in* t#e te't' for nitro*en/ '!%p#!r $n #$%o*en'. An or*$ni" "ompo!n "ont$inin* C/ E/ N/ S $n #$%o*en' )#en f!'e )it# 'o i!m met$% *i+e' t#e fo%%o)in* re$"tion'.
fusio&

C + N + N a Prese&t i& orga&i# so$ium#-a&i#e #om%ou&$ NaCN X(C1, Br, I) + Na

from orga&i# Won )W From so$ium wm%ou&$ ali$e

NaX (X--CI, Br, Ij S + 2Na

fusio& So$ium sul% i$e #om%ou&$ Na-s

from orga&i#

6N$SC118 i' forme !rin* f!'ion/ )#i"# in t#e pre'en"e of ex"e'' 'o i!m form' 'o i!m "&$ni e $n 'o i!m '!%p#i e.
fusio&

Na+C+,N+S

i& orga&i# #om%ou&$

NaCNS

so$ium t io#-a&ate

-,,ar NaCNS + 2Na

i& orga&i# #om%ou&$ fusio&

NaCN + Na2S
so$ium .iio#-a&ate

7. Dete"tion of Nitro*en A 'm$%% .!$ntit& of t#e 'o i!m extr$"t i' t$(en in $ te't t!,e. It i' m$ e $%($%ine ,& $ in* 1-7 rop' of 'o i!m #& roxi e 6N$OE8 'o%!tion. 1 mL of fre'#%& prep$re 'o%!tion of ferro!' 'Ip#$te i' $ e to t#i' 'o%!tion. T#e mixt!re of t#e t)o 'o%!tion' i' ,oi%e $n t#en $"i ifie )it# i%!te '!%p#!ri" $"i . T#e $ppe$r$n"e of pr!''i$n ,%!e or *reen "o%o!r$tion of t#e pre"ipit$te "onfirm' t#e pre'en"e of nitro*en in t#e *i+en or*$ni" "ompo!n . T#e "$r,on $n nitro*en pre'ent in t#e or*$ni" "ompo!n on f!'ion )it# 'o i!m met$% *i+e 'o i!m "&$ni e 6N$CN8 'o%!,%e in )$ter. So/ t#e 'o i!m extr$"t "ont$in' 'o i!m "&$ni e )#i"#/ on re$"tion )it# ferro!' '!%p#$te/ *i+e' 'o i!m. ferro"&$ni e. Some of t#e ferro!' '$%t i' oxi i'e to t#e ferri" '$%t on #e$tin* $n t#i' re$"t' )it# 'o i!m ferro"&$ni e t$ form feiri" ferro"&$ni e. 6NaCN + FeS04 3 Na4(Fe(CN)6] + 2Fe2(SO4)3
form ! !ur"#$ %o"&"#$ of '( )o&u'"o#

fusion fusion

Na,rjFe(CN)d + Na2S04 )o!"um '

No' -

mo*+a#"!

Fe4('Fe(CN)d3 + 6Na2S04 ,ru)"a# %&u When nitrogen and sulphur both are present in any organic compound, sodium thiocyYrnate is formed during fusion. When extracted with water sodium thiocyanate goes into the sodium extract and gives 'blood red coloration' with ferric ions due to the formation of ferric thioc"nate
Na+C+N+S

NaCNS
From organic
1o# -

sodium thiacymiate compound

. (2S)3 + 3Na3

3NaCNS + . /0

(mood red) t Dete"tion of S!%p#!r T#e pre'en"e of '!%p#!r in $n& or*$ni" "ompo!n i' ete"te ,& !'in* 'o i!m extr$"t $' fo%%o)'B Le$ A"et$te Te't 618. A 'm$%% portion of 'o i!m extr$"t i' $"i ifie )it# $"eti" $"i $n %e$ $"et$te 'o%!tion i' $ e to it. A ,%$"( pre"ipit$te of %e$ '!ip#i <Hn i"$te' t#e pre'en"e of '!%p#!r.
Fentethl ocyanato

An So i!m N@t%ropr!''i e Te't 618/ to $ 'm$%% .!$ntit& of 'o i!m extr$"t t$(en in $ te't t!,e/ 1 to 7 rop' of 'o i!m nitropr!''i e $re $ e to t#e 'o%!tion. A +io%et "o%or in i"$te' t#e pre'en"e of '!%p#!r. T#i' "o%or f$ e' $)$& '%o)%& on 't$n in*. Na2,S + Na2 !e(CN)"#$%& -...o-.. Na4Fe(CN)S1V0d
)o!&ur# #Xr,ru))"! 4&o& r *o%r

(CH3C00) !" + Na2#S

,## 'b + 2C( )C** Na $%e6I 5r#'! ,#C67a'

3

& a! a* 'a'

"# )o!"um