Expt # 8B: Qualitative Analysis Bacareza, Maxine Nicole Guiez, Abigail Ann A.

HEJ1, Group # 9, Mr. Jason Vedad Date Submitted: March 1, 2012

I. Abstract Qualitative analyses of test samples of alcohols and phenols, aldehy
des and ketones, amines, and carboxylic acid and its derivatives were done. Sodi
um metal test, Lucas test, and potassium test were used for the identification a
nd differentiation of alcohols. Ferric chloride test, bromine water test, and Mi
llons Test were used for the analyses of phenols. Eight tests, namely 2,4-DNPH te
st, Bisulfite test, Schiffs test, Tollens test, Iodoform test, Fehlings test, Molis
ch Test, and Benedicts Test were used to identify and differentiate aldehydes and
ketones. Aldehydes are more reactive to tests than ketones. The presence and di
fferentiation of amines were tested using Hinsberg test where 1, 2, and 3 amines re
acted differently, allowing for its differentiation. The formation of esters, hy
drolysis of the acid derivatives: benzamide, ester, and anhydride were observed
and hydroxamic acid test was used for the presence of carboxylic acid and its de
rivatives. II. Keywords: Qualitative Analysis, Alcohol, Phenol, Ketone, Aldehyde
, Amine, Acid Derivatives III. Introduction Chemists must regularly identify com
pounds that are formed in reactions or found in natural resources. In order to d
o this, chemists must classify the functional groups present in an unknown compo
und for successful identification of its identity and its properties. The most c
ommonly used methods for qualitative analyses of organic substances are chemical
and spectroscopic methods. In this experiment, the focus is on the use of chemi
cal methods in identifying and differentiating various organic compounds. Differ
ent tests with different specific reactions to different functional groups are u
sed to successfully identify the compound being analyzed. The typical indicators
for positive test results are a change in the color of solution and the formati
on of precipitates. Tests are also used to differentiate types of compounds cont
aining the same functional group based on the rate of the reaction and formation
and dissolution of precipitates. IV. Experimental E. Tests for Alcohols and Phe
nols 1. Reaction of Alcohols 1.1 Reaction with Sodium Metal Twenty drops of n-bu
tyl alcohol were placed in a 5mL test tube. A piece of sodium metal was carefull
y added. The evolution of bubbles was observed. The test was repeated with sec-b
utyl alcohol and tertbutyl alcohol. The relative rates of bubble formation were
compared. 1.2 Lucas Test Twenty drops of Lucas reagent and 10 drops were placed
in a 5-mL test tube. The test tube was Chemistry 31.1, Qualitative Analysis 2.2
Bromine Water Test Twenty drops of 95% ethanol and 5 drops of liquid phenol were
placed in a 5-mL test tube. Bromine water was added dropwise while being shaken
until the color of bromine persisted. Observations were recorded. The procedure
was repeated for n phthol, c techol, nd resorcinol. 2.3 Millons Test Five drops
e ch of Millons re gent nd phenol were pl ced in
5-mL test tube. The test tube
w s sh ken nd he ted in
w ter b th for 2 minutes. Observ tions were recorded
. The procedure w s repe ted for -n phthol, c techol, nd resorcinol. F. Tests of
Aldehydes nd Ketones P ge 1 of 13 sh ken vigorously nd covered with stopper
. The form tion of n insoluble l yer w s observed nd timed. The procedure w s
repe ted using sec-butyl lcohol nd tert-butyl lcohol. The rel tive r tes of l
yer form tion were comp red. 1.3 Re ctions with Pot ssium Dichrom te Twenty dro
ps of n-butyl lcohol were pl ced in
5mL test tube. The solution w s cidified
with 2M H2SO4. Five drops of 3% K2Cr2O7 solution w s dded. Observ tions were r
ecorded. The procedure w s repe ted for sec-butyl lcohol nd tert-butyl lcohol
. 2. Re ctions of Phenol 2.1 Ferric Chloride Test Twenty drops of 95% eth nol n
d 5 drops of liquid phenol were pl ced in
5-mL test tube. Five drops of 3% FeC
l3 solution w s dded nd mixed. Observ tions were recorded. The procedure w s r
epe ted for -n phthol, c techol, nd resorcinol.

1. 2,4-DNPH Test Five drops of 2,4-DNPH soluiton nd 3 drops of form ldehyde wer
e pl ced in 5-mL test tube. The test tube w s he ted in
w ter b th for 5 min
utes. Observ tions were recorded. The test w s repe ted for cet ldehyde, ceton
e, nd benz ldehyde. 2. Bisulfite Test Twenty drops of sodium bisulfite nd 5 dr
ops of form ldehyde were pl ced in
5-mL test tube. The contents were mixed tho
roughly. The test tube w s pl ced in n ice b th. Observ tions were recorded. Th
e test w s repe ted for cet ldehyde, cetone, nd benz ldehyde. 3. Schiffs Test
Twenty drops of Schiffs re gent nd 5 drops of form ldehyde were pl ced in
5-mL
test tube. Observ tions were recorded. The test w s repe ted for cet ldehyde,
cetone, nd benz ldehyde. 4. Tollens Test Twenty drops of Tollens re gent nd 5 d
rops of form ldehyde were pl ced in 5-mL test tube. The test tube w s he ted i
n w ter b th. Observ tions were recorded. The test w s repe ted for cet ldehy
de, cetone, nd benz ldehyde. 5. Iodoform Test Twenty drops of 10% N OH nd 5 d
rops of form ldehyde were pl ced in 5-mL test tube. KI/I2 solution w s dded d
ropwise, while being mixed until the brown color of I2 persisted. The test tube
w s he ted in w ter b th t 60C for 2 minutes. Ten percent N OH solution w s d
ded dropwise with mixing until the brown color of I2 dis ppe red nd yellow co
lor persisted. Five drops of distilled w ter were dded. The test tube w s sh ke
n vigorously. The test tube w s llowed to st nd for 15 minutes. Observ tions we
re recorded. The test w s repe ted for cet ldehyde, cetone, nd benz ldehyde.
6. Fehlings Test Twenty drops of Fehlings re gent nd 5 drops of form ldehyde were
pl ced in 5-mL test tube. The test tube w s he ted in
w ter b th. Observ ti
ons were recorded. The test w s repe ted for cet ldehyde, cetone, nd benz lde
hyde. 7. Molisch Test Twenty drops of Molisch re gent nd 5 drops of % glucose
were pl ced in 5-mL test tube. The test tube w s inclined. Two mL of concentr
ted H2SO4 w s run down through the sides of the test tube. The test tube w s c r
efully brought to n upright position. The form tion of blue-violet ring w s C
hemistry 31.1, Qu lit tive An lysis
observed. The test w s repe ted using 1% m ltose, 1% sucrose, nd 1% boiled st r
ch. 8. Benedicts Test Twenty drops of Benedicts re gent nd 5 drops of 1% glucose
were pl ced in 5-mL test tube. The test tube w s he ted in
w ter b th. Ch ng
es were observed for. The test w s repe ted using 1% m ltose, 1% sucrose, nd 1%
boiled st rch. G. Test for Amines Hinsberg Test Twenty drops of 10% N OH, 5 dro
ps of methyl mine, nd 5 drops of benzenesulfonyl chloride were pl ced in
5-mL
test tube. The test tube w s covered with stopper nd sh ken for 5 minutes. T
he solution w s tested using litmus to see if it w s b sic. Ten percent N OH w s
dded dropwise until the solution w s b sic to litmus. If precipit te w s obs
erved to form, 40 drops of w ter w s dded. The solution w s sh ken. Observ tion
s were recorded. To the result in the previous step, 3M HCl w s dded dropwise w
hile the solution w s being mixed. The procedure w s repe ted using dimethyl min
e, trimethyl mine, niline, nd nmethyl niline. H. Test for C rboxylic Acid nd
its Deriv tives 1. Form tion of Esters Re ction of C rboxylic Acid nd Alcohol A
pinch of s licylic cid nd 20 drops of meth nol were mixed in
10-mL test tub
e. Five drops of concentr ted H2SO4 w s dded. The mixture w s sh ken nd he ted
in w ter b th for 5 minutes. Observ tions were recorded. 2. Hydrolysis of Aci
d Deriv tives 2.1 Hydrolysis of Benz mide A pinch of benz mide nd 20 drops of 1
0% N OH were pl ced in
5-mL test tube. A piece of moist red litmus p per w s h
eld, using stirring rod, bove the mouth of the test tube while the l tter w s
being he ted to boiling in w ter b th. Ch nges in the color of the litmus p p
er nd in the odor of the mixture were noted. 2.2 Hydrolysis of n Ester Twenty
drops of ethyl cet te were pl ced in 5-mL test tube. Five drops of 25% N OH so
lution were dded. The test tube w s loosely covered with stopper nd he ted
in w ter b th for 15 minutes. A 1M solution of HCl w s dded dropwise until th
e solution w s neutr l to litmus. Ch nges in the odor of the mixture were noted.
P ge 2 of 13

2.3 Hydrolysis of n Anhydride Twenty drops of w ter nd piece e ch of red nd

blue litmus p pers were dded to 5-mL test tube. Twenty drops of cetic nhyd
ride were c refully dded. The tube w s gently sh ken nd felt. Observ tions wer
e recorded. 3. Hydrox mic Acid Test for Acid Deriv tives Five drops of ethyl cet
te nd 20 drops of 7% meth nolic hydroxyl mine hydrochloride solution were dde
d to 5-mL test tube. The cidity/b sicity of the solution w s tested using red
litmus p per. Ten percent meth nolic KOH w s dded until red litmus p per turne
d blue, then ten more drops w s dded. The solution w s he ted to boiling in w
ter b th nd w s llowed to slightly cool. Ten drops of 3% FeCl3 w s dded. Obs
erv tions were recorded. The procedure w s repe ted for benz mide, cetic nhydr
ide, nd benzoylchloride. V. Results
sec-butyl lcohol
tert-butyl lcohol
Single l yer:

sp r gus greend rkBG Single l yer: golden brown

Cr
3+
Cr2O7
22. Re ction of Phenols
T ble 4: Ferric Chloride Test
S mple
Phenol
C techol Resorcinol -n pthol
Visible Result D rk brown; no ppt; sep r tes into lighter bove, d rker below D
rk blue w/ no ppt Olive green w/ d rk l yer t bottom Purplish bl ck w/ powders
(d rker)
Formul Fe(OAr)3
Fe(OAr)3 Fe(OAr)3
Fe(OAr)3
E. Tests for Alcohols nd Phenols 1. Re ction of Alcohols
T ble 1: Re ction with N met l
Bromine w ter test w s not conducted due to l ck of re gents. But this is the th
eoretic l result:
T ble 5: Bromine W ter Test
S mple n-butyl lcohol sec-butyl lcohol tert-butyl lcohol
Visible Result Evolution of g s Evolution of g s Evolution of g s
Formul H2 H2 H2
S mple Phenol C techol Resorcinol
Visible Result Light Brown D rk solution

Formul 2,4,6tribromophenol Bromin tion of benzene Ring Tribromoresorcinol 2,4-d

ibromo-1n phthol
R te of evolution of g s: n-buty lcohol>sec-buty lcohol >tert-buty lcohol
T ble 2: Luc s Test
S mple n-butyl lcohol sec-butyl lcohol
tert-butyl lcohol
Visible Result No ch nge Form tion of l yers Cle r to light blue
Formul n/
CH3CHClCH2CH3 + H2O (CH3)3CCl + H2O
-n pthol
Yellow with ppt D k cloudy solution
T ble 6: Millons Test
S mple Phenol C techol
R te of form tion of insoluble l yer: tert-buty lcohol>sec-buty lcohol >n-buty l
cohol
T ble 3: Re ction with Pot ssium Dichrom te
Visible Result More viscous th n -n pthol; d rk brown Bl ck Prior to melting: bro
wnish yellow w/ sm ll suspended p rticles; fter he ting: brownish or nge w/ mor
e
Formul Hg complex with Phenols Hg complex with Phenols Hg complex with Phenols
S mple
n-butyl lcohol
Visible Result Ring: brown greend rkBG; nd 2 l yer: d rk yellowgreen cle r; Bottom:
or nged rk greend rkBG
Formul Cr
3+
Resorcinol
Chemistry 31.1, Qu lit tive An lysis
P ge 3 of 13

-n pthol
suspended p rticles Viscous brown; smells like burned pl stic
Hg complex with Phenols
Acet ldehyde Acetone Benz ldehyde S mple
Yellow ppt Yellow ppt No ch nge Visible Result Turned or nge w/ d rk brown ppt
t bottom Brick-red ppt No ch nge Tr nslucent yellow green cloudy or nge l yer Feh
lings: roy l bluebrown
CHI3 CHI3 n/ Formul

Cu2O Cu2O n/ Cu2O

T ble 12: Fehlings Test

F. Tests of Aldehydes nd Ketones Form ldehyde
T ble 7: 2,4-DNPH Test
S mple Form ldehyd e Acet ldehyde
Visible Result Yellow ppt
Formul 2,4dinitrophenylhydr zone 2,4dinitrophenylhydr zone (theoretic l) 2,4d
initrophenylhydr zone 2,4dinitrophenylhydr zone
Acet ldehyde Acetone
Acetone
Benz ldehyde
Or nge, brown (when he ted) Yellow color; ppt did not dissolved Or nge color; 2
l yers; ppt dissolved Visible Result Ppt form tion Ppt form tion No ppt Ppt form
tion Visible Result Turned d rk violet Red-purple purple
Benz ldehyde
T ble 13: Molisch Test
S mple
Glucose
Visible Result (+) violet ring (++) violet ring (+++) violet ring
Formul
T ble 8: Bisulfite Test
S mple Form ldehyde Acet ldehyde Acetone Benz ldehyde
T ble 9: Schiffs Test
Formul H2CH(OH)SO3 + N + H3C(OH) SO3 N H3CC(OH)SO3 + N (C6H6)CH(OH)SO3 + N
Formul
M ltose
Sucrose

Boiled st rch
Violet ring
S mple Form ldehyd e Acet ldehyde Benz ldehyde Acetone S mple Form ldehyde Acet
ldehyde Acetone Benz ldehyde S mple Form ldehyde
T ble 14: Benedicts Test
S mple Form ldehyde Acet ldehyde Acetone
No ch nge
n/ Formul Ag Ag n/ Ag Formul n/
Benz ldehyde
Visible Result (++) brick red l yer (+++) brick red l yer (+) brick red l yer () no ch nge
Formul Cu2O Cu2O Cu2O n/
T ble 10: Tollens Test
G. Tests for Amines
T ble 15: Hinsberg Test
Visible Result Silver mirror Silver mirror cle r Silver mirror Visible Result No
ch nge
S mple Methyl mine Dimethyl mine Trimethyl mine Aniline
Visible Result ppt in cid ppt in b se/ cid ppt in b se ppt in b se/ cid
Formul C6H5SO2NRH C6H5SO2NR2 R3NHCl C6H5SO2NRH
T ble 11: Iodoform Test
Chemistry 31.1, Qu lit tive An lysis
P ge 4 of 13

N-methyl niline
ppt in

cid

C6H5SO2NRH
H. Test for C rboxylic Acid nd its Deriv tives 1. Form tion of Esters
T ble 16: Re ction of C rboxylic Acid nd Alcohol
determin tion f ctor. It h s been observed th t b sed on the r te of bubble form
tion, it would be possible to differenti te between prim ry, second ry nd tert
i ry lcohols. B sed on the experiment, it c n be inferred th t the more cidic
n lcohol is, the f ster the r te of bubble form tion. Thus, n-buty lcohol>secbuty lcohol >tert-buty lcohol. Luc s test: This test is lso used to distinguish
mong prim ry, second ry, nd terti ry lcohols. The re gent used is mixture
of concentr ted Hydrochloric Acid (HCl) nd Zinc Chloride (ZnCl2), which on re c
tion with OHs converts them to the corresponding lkyl chlorides. R ther th n fo
cusing on the r te of bubble form tion, this test focuses m inly on the speed in
which n insoluble l yer is formed. A positive test depends on the f ct th t th
e lcohol is soluble in the re gent, where s the lkyl chloride is not; thus the
form tion of second l yer or n emulsion constitutes
positive test. But the
solubility of the lcohol in the re gent limits the test in gener l to monofu
nction l lcohols lower th n hexyl nd cert in polyfunction l molecules. Alcohol
s, depending on their structure, forms v ried c rboc tions or species cont ining
positively ch rged c rbon. It is expected for n lcohol with 30 c rboc tio
n to form n lkyl h lide the f stest bec use it is the most st ble. H logen tio
n is the process which t kes pl ce when lcohols re ct with the Luc s solution o
r ZnCl2 solution in concentr ted HCl. When the lcohols re ct, the H+ from HCl w
ill proton te the OH group of the lcohol. W ter will then le ve since it is
w
e ker nucleophile th n OH. When w ter le ves, the nucleophile Cl- will be substi
tuted for it.
S mple S licylic Acid
Visible Result Mixed upon he ting; cloudy
Formul
2. Hydrolysis of Benz mide
T ble 17: Hydrolysis of Benz mide
S mple Benz mide
Visible Result Smells like

mmoni Visible Result Strong sour odor

Formul NH3
T ble 18: Hydrolysis of Ester
S mple Ethly cet te
Formul

CH3COOH

T ble 19: Hydrolysis of Anhydride

S mple Acetic Anhydride
Visible Result Blue litmus to red; sour odor
Formul CH3COOH

3. Hydrox mic Acid Test

T ble 20: Hydrox mic Acid Test
S mple Ethyl cet te Benz mide Acetic Anhydride Benzoylchloride
Visible Result Wine-red Bet dinecolored red Blood-red Blood-red
Formul Hydrox m te complexes Hydrox m te complexes Hydrox m te complexes Hydrox
m te complexes
VI. Discussion E. Tests for Alcohols nd Phenols 1. Re ction of Alcohols Re ctio
n with N met l: The re ction of n lcohol with sodium met l is simil r s to s
odium met ls re ction with w ter given by the equ tion: which produces hydrogen g
s nd sodium hydroxide. In this re ction, the cidity of the lcohol is prim
ry Chemistry 31.1, Qu lit tive An lysis
This type of unimolecul r nucleophilic substitution is c lled SN1. The re ction
r te is much f ster when the c rboc tion intermedi te is more st bilized by
gr
e ter number of electron-don ting lkyl group bonded to the positive c rbon tom
. This me ns th t the gre ter the lkyl groups present in
compound, the f ster
its re ction would be with the Luc s solution. Thus prim ry lcohols do not re
ct ppreci bly with HCl even in the presence of ZnCl2 t ordin ry temper tures;
the prim ry c rbonium ion is too unst ble to serve s n intermedi te in the
P ge 5 of 13

c rbonium ion mech nism. However, the high re ctivity of terti ry lcohols (wher
ein the lkyl h lide is visible within
few minutes t room temper ture) is
c
onsequence of the rel tively gre t st bility of the intermedi te c rbonium ion.
Theoretic lly, sec-butyl lcohol would re ct in bout 5 minutes while prim ry l
cohols do not ppreci bly re ct with the Luc s re gent t room temper ture. Re c
tion with Pot ssium Dichrom te:
excess of the oxidizing gent. Ag in by using eth nol to form eth noic cid: Sec
ond ry lcohols, on the other h nd, only get oxidized s f r s being ketone.
No m tter wh t the re ction conditions re, ketones re the endpoint for the oxi
d tion of second ry lcohols. To illustr te:
Another test to differenti te prim ry, second ry nd terti ry lcohols would be
to use their re ctive selectivity s b sis. This test is the re ction with pot
ssium dichrom te. Scientists consider this s the most reli ble since it could
llow ccur te differenti tion of the lcohols. Pot ssium dichrom te requires n
lcohol to h ve
H+ tt ched to the hydroxide group to be ble to oxidize it.
Since terti ry lcohols do not h ve this H+ tom, they do not re ct with the dic
hrom te ion. The prim ry nd second ry lcohols would be the only one to re ct w
ith the pot ssium dichrom te nd th t they c n lso be differenti ted s they wo
uld produce different products during oxid tion. Prim ry lcohols re gener lly
the most re ctive with pot ssium dichrom te. When they first become oxidized, th
ey become ldehydes. On the second oxid tion, the ldehydes become c rboxylic c
ids. B sic lly, prim ry lcohols re oxidized into both ldehydes nd c rboxylic
cids depending on the re ction conditions. Prim ry lcohols become oxidized in
to ldehydes when there is n excess mount of the lcohol. Wh t h ppens is th t
there is l ck of oxidizing gent to fully convert the lcohol. To underst nd
the phenomenon, the electron h lf equ tion is:
The O between the c rbon nd hydrogen in the ldehyde group to form c rboxylic
cid w s present. Now, the hydrogen is nowhere signifying th t the re ction end
s there. Terti ry lcohols re gener lly unre ctive with pot ssium dichrom te. T
his is bec use the oxidizing gent h s nothing to remove. In prim ry lcohols, t
he gent c n remove the hydrogen from the OH group. In second ry lcohols, the g
ent removes hydrogen from the c rbon tom tt ched to the OH. Terti ry lcohols
dont h ve such. Illustr ting this:
2. Re ctions of Phenols Ferric Chloride Test: Most phenols cre te re ction wit
h iron (III) chloride to form colored complex. The colors v ry, depending not
only on the n ture of the phenol but lso on the solvent, concentr tion, nd tim
e of observ tion. Some phenols th t do not give color tion in queous or lcohol
ic solution do so in chloroform solution, especi lly fter ddition of drop of
pyridine.
The lcohol used is eth nol nd when this equ tion is further simplified which s
hows O s the oxidizing gent to form eth n l:
The second illustr tion is the more visu l ppro ch tow rds underst nding the fu
ll re ction in the form tion of n ldehyde. As w s s id, prim ry lcohol c n
lso be further oxidized into c rboxylic cid. This h ppens when there is n
The n ture of the colored complexes is still uncert in; they m y
xide s lts th t bsorb visible light to give n excited st te in
re deloc lized over both the iron toms nd the conjug ted org
production of color is typic l of phenols; however, m ny of P
Chemistry 31.1, Qu lit tive An lysis

be ferric pheno
which electrons
nic system. The
ge 6 of 13

them do not give colors, so neg tive feric chloride test must not be t ken s
signific nt without supporting inform tion. Bromine W ter Test: With the s me i
m s the ferric chloride test, the bromine w ter test detects the presence of ph
enol nd phenolic groups. The tt ched OH groups on the benzene ring re more re
ceptive to electrophilic re gents s they c n ccommod te them. Therefore, s
phenol is mixed with bromine, it would undergo bromin tion. To check if the test
for the presence of phenol is positive, bromine would decolorize nd th t the m
ixture would yield precipit tes. Both lkenes nd phenols re ct with bromine w t
er. In both c ses, there will be signific nt color ch nge from or nge to color
less. There will be decoloroz tion of bromine nd this would signify th t the
function l group OH tt ched directly to the benzene ring. A susbstitution re cti
on is expected of the phenol re cting with bromine. The product, 2,4,6tribromoph
enol, is formed. Such product is c lled
tribromin ted product. The benzene rin
g in phenol is much more re ctive th n norm l benzene ring bec use of the hydr
oxyl group tt ched to it:
mercurous ions in nitric nd nitrous cids, the visible result would be white
precipit te long with red solution since there is form tion of mercury s lt
s fter he ting. F. Tests of Aldehydes nd Ketones 2,4 DNPH Test: The re gent, 2
,4dinitrophylhydr zine or 2,4-DNPH, re cts with the c rbonyl groups of ldehydes
nd ketones. The re ction is given:
Re ction of 2,4-DNPH
It is import nt to note th t even if there is subsequent decoloriz tion of the
bromine, the re ction observed would still be substitution re ction r ther th
n n ordin ry ddition of
norm l lkene. The difference between phenols re c
tion with th t of n lkene is quite observ ble. Both compounds would yield
de
coloriz tion of the bromine w ter but for phenols, the tribromin ted product is
formed. This would be quite observ ble s white precipit te which forms just
fter the decoloriz tion itself. In ddition, HBr will be gener ted but will not
be observed since the re gent is queous. Millons Test: The l st test for phenols
is the Millons test. The structure of the re gent is (Hg(NO3))2 in H2O. It h s b
een observed th t positive test h s pink to red colored solution or precipit
te. However, this test m y h ve v rying experiment l results since some phenols
such s c techol nd resorcinol do not effectively form compound with
free
OH group. To detect the presence of hydroxyphenyl group (phenolic-OH), this te
st is then pplied. Since Millons re gent is m de up of mercuric nd Chemistry 31
.1, Qu lit tive An lysis
2,4-DNPH detects the presence of ldehydes nd ketones by repl cing the oxygen
tom tt ched to c rbon tom by
double bond. The form tion of yellow-or nge-r
ed precipit te indic tes positive result for n ldehyde or ketone. Sm ll, unc
onjug ted ldehydes nd ketones form close to yellow precipit tes while l rge, c
onjug ted ldehydes nd ketones form close to red precipit tes. The form tion of
n oily l yer should lso be noted s some ketones ( nd lso enols) form oils t
h t do not solidify or precipit te fter the re ction of 2,4-DNPH. The 2,4-DNPH
test is considered the simplest test for ldehydes nd ketones but it c n lso l
e d to misle ding results nd d t . For inst nce, excess cid c t lyst m y resul
t to the re ction of the cid with 2,4-DNPH th n with the test s mple. Using imp
ure lcohols m y le d to in ccur te results s this might cont in ldehyde or ke
tone impurities. Thus, other qu lit tive tests re lso employed together with t
his test. Bisulfite Test Aldehydes nd unhindered ketones dd bisulfite to form
w ter insoluble ddition compounds. An ex mple of the re ction is given by:
Re ction of Bisulfite A more det iled discussion of the ch r cteristic re ction
of ldehydes nd ketones expl ins th t b se-c t lyzed nucleophilic ddition oc
curs cross the c rbon-oxygen double bond. The c rbon tom of the c rbonyl group
then cquires p rti l positive ch rge s the C=O bond is pol rized. The bisul
fite ion, HSO3 , is n electron P ge 7 of 13

rich nd consequently strong nucleophile. Thus it re dily tt cks the p rti ll

y positive c rbon tom of the c rbonyl group. The oxygen tom is oxidized into
hydroxide ion, OH , by the bisulfite ion which then bonds with c rbon to form t
he w ter soluble precipit te. Moreover, this test lso differenti tes ldehydes
nd ketones through the r te of re ction. Aldehydes re more re ctive to ketones
in the bisulfite test due to steric nd inductive effects present in ketones. A
s shown in the figure below, the presence of bulky lkyl groups steric lly hinde
rs the nucleophile from ppro ching the c rboc tion. Moreover, lkyl subsituents
which re we k electron don ting groups m ke the c rbonyl tom less electrophil
ic. These f ctors le d to slow form tion of precipit tes or the bsence of preci
pit te in ketones.
Tollens Test: This test is nother test for ldehydes. Tollens re gent consists of
silver di mine complex which is responsible for the form tion of silver mirr
or in the presence of n ldehyde. The re ction is given by:
Re ction of Tollens Re gent The silver di mine complex is reduced by ldehyde to
met llic silver which is observed s the form tion of silver subst nce simil r
to mirror. Tollens re gent lso re cts with triple bonds nd c n produce the s
me results s ldehydes nd thus c n le d to in ccur te results. Iodoform Test:
Iodoform test is cl ssic l test for methyl ketones. However, it c n lso give
positive results for cet ldehyde, eth nol, nd other second ry lcohols. Secon
d ry lcohols with n dj cent methyl group c n be oxidized by iodine ble ch int
o methyl ketones. The re ctions re given by:
Steric Hindr nce in C rbonyl C rbon
Electrophilic Ch r cter of C rbonyl C rbon Schiffs Test: Schiffs test is specific
lly used for the differenti tion of ldehydes nd ketones s the r te of re ctio
n of the Schiffs re gent differs gre tly for ldehydes nd ketones. Schiffs re gen
t, pink triphenylmeth ne dye which is converted into
colorless leucosulfonic
cid by sulfurus cid, is known s fuschine or p-ros niline hydrochloride. It r
e cts mostly with ldehydes by the s me re sons st ted bove for ketones with bu
lky lkyl groups nd substituents with we k electron don ting groups. The re cti
on of Schiffs re gent with n ldehyde is given by:
Re ction of Iodine
Oxid tion of Second ry Alcohols into Methyl Ketones The re gent in n iodoform t
est cont ins I2 in KI solution. In b sic solution, the hydrogen toms of the c r
bon next to the c rbonyl group re repl ced by iodine to produce tri-iodo-methyl
c rbonyl compounds, s shown below. In the next firgure, the tri-iodo-methyl co
mpound then re cts with OH to form iodoform nd c rboxylic cid or s lt.
Re ction of Schiffs Re gent The bisulfite ion present in the re gent produces n
sp3 hybridiz tion. The ldehyde re cts simil rly in the bisulfite test nd is ox
idized into n lcohol, displ cing the bisulfite nd ch nging the hybridiz tion
to sp2. The ppe r nce of
purple color indic tes positive result for the Sch
iffs test.
Re ction of Methyl Ketone nd Iodine
Re ction of Tri-iodo-methyl nd OH Chemistry 31.1, Qu lit tive An lysis
P ge 8 of 13

The form tion of yellow precipit te with cryst l-like ppe r nce indic tes p
ositive result for the iodoform test. Fehlings Test: Fehlings test is nother test
for the presence of ldehydes nd is lso used for tests for the presence of su
g rs since sug rs, when dehydr ted re ctu lly ldehydes ( ldoses). A positive
result shows the form tion of brick red precipit te which is ctu lly c used b
y the form tion of Cu2O. The re ctions involved re given below:
the form tion of the precipit te Cu2O. This test llows for the identific tion o
f sug rs th t h ve the bility to reduce cupric ion to cuprous oxide. The re cti
on is given below:
Re ction in Benedicts Test G. Test for Amines Hinsberg Test: Hinsberg test is use
d to differenti te prim ry, second ry nd terti ry mines nd nilines depending
on the solubility of the precipit te or oily l yer which would form from the re
ction. In this test, benzenesulfonyl chloride is used s re gent present s ins
oluble oil in n queous b sic solution. Prim ry mines dissolve in b se nd pre
cipit tes from cidic solutions. Second ry mines precipit te from b se nd no c
h nge is observed in cid. Terti ry mines precipit te from b se nd dissolves i
n cid. The re ctions re given below:
Re ctions in Fehlings Test This test is very sensitive th t even minute mounts o
f ldehydes or c rbohydr tes c n result to the brick red color of the compound.
Molisch Test: The Molisch test is used to test for the presence of c rbohydr tes
. The dehydr tion of c rbohydr tes through sulfuric cid produces n ldehyde. T
he form tion of purple ring indic tes positive result. It is result of the
dehydr ted c rbohydr te condensing with n phthol. The re ctions re given by:
Re ctions for 1, 2, nd 3 Amines
S mple Re ction in Molisch Test Thus, it is specific lly instructed not to sh ke
the test tube cont ining the test s mple so s not to disturb the purple ring t
h t forms in the presence of n ldehyde or c rbohydr te. Benedicts Test: Benedic
ts test is test employed in the identific tion of the presence of glucose. Simi
l r to Fehlings test, positive result is given by the ppe r nce of brick red c
olor due to Chemistry 31.1, Qu lit tive An lysis
H. Test for C rboxylic Acid nd its Deriv tives 1. Form tion of Esters Re ction
of C rboxylic Acid nd Alcohol: An ester is product of the re ction of n cid
(usu lly org nic) nd n lcohol (the hydrogen of the cid R-COOH is repl ced b
y n lkyl group R
). Esters m inly result from the condens tion ( re ction th
t produces w ter) of c rboxylic cid nd n lcohol. The process is c lled est
erific tion. The esterific tion re ction is both slow nd reversible. To h ve
positive test, the re ction must be subjected to he t (the re ction is s id to b
e endothermic nd th t n incre se in he t c uses more collision) nd n cid c
t lyst, H2SO4 in this c se, to f vor forw rd re ction. Ester, in big mount, giv
es off fruity smell. When s licylic cid combines with meth nol it becomes the
ester known s methyl s licyl te or oil of wintergreen. Meth nol is lso known
s methyl lcohol nd wood lcohol. The P ge 9 of 13

re ction of s licylic cid C6H4 (OH) CO2H

nd meth nol CH3OH forms this ester.

hydroxide group nd elimin tion of mide ion. When he ted with

moni g s is given off.

b se (N OH), m

2. Hydrolysis of Acid Deriv tives Hydrolysis re ctions re s id to be cidc t ly

zed or b se-c t lyzed. In the over ll process of hydrolysis, bond in n org ni
c molecule is broken (for cid deriv tives, forming n cyl group), nd n O-H b
ond in w ter molecule lso bre ks. Then, from the w ter molecule, n O-H group
dds to one p rt from the org nic molecule, nd n H tom to the other.
In the experiment, the b se-c t lyzed re ction w s performed th t yielded to the
mmoni odor th t w s observed. Hydrolysis of n Ester: The hydrolysis of ester
in cidic nd lk line conditions is represented below:
B se-c t lyzed is
one w y re ction while the cid-c t lyzed is reversible. The
products of the former re e sier to sep r te (sodium s lt is formed r ther th
n c rboxylic cid itself, to obt in the c rboxylic cid, dilute cid must be dd
ed fter distilling the other product), while th t l tters c nt be sep r ted e sil
y thus h rder to test.
Notice th t in lk line conditions, the c rboxyl te ion is formed. The ddition
of strong cid, such s dilute HCl, is required to free the c rboxylic cid mo
lecule. In the b se-c t lyzed hydrolysis bove, you could think of the re ction
s with w ter, nd the c rboxylic cid molecule formed losing proton to
hydr
oxide ion. A strong sour odor will be observed due to the form tion of cetic c
id. Hydrolysis of n Anhydride: Anhydrides re deriv tives of c rboxylic cids.
All deriv tives of c rboxylic cids c n be converted to the corresponding cid t
hrough re ction with w ter. Some less re ctive deriv tives require c t lyst fo
r the re ction to occur in re son ble time, but nhydrides do not. In the hydr
olysis of n nhydride, w ter tt cks the nhydride in nucleophilic substituti
on. The solution obt ined from this re ction turns blue litmus to red due to con
version to cid.
Hydrolysis of Benz mide: Benz mide is less re ctive th n cid chlorides, cid n
hydrides, or esters. It undergoes hydrolysis to yield c rboxylic cids plus min
e on he ting in either queous cid or queous b se. In cid-hydrolysis, there i
s nucleophilic ddition of w ter to the proton ted mide, followed by the loss
of mmoni .
On the other h nd, in
b sic solution, there is nucleophilic ddition of hydr
oxide to the mide c rbonyl group, followed by the deproton tion of the Chemistr
y 31.1, Qu lit tive An lysis
3. Hydrox mic Acid test for Acid Deriv tives
P ge 10 of 13

Hydrox mic cid is

cl ss of chemic l compounds sh ring the s me function l gro
up in which hydroxyl mine is inserted into c rboxylic cid. In the Hydrox mi
c Test for cid deriv tives, hydroxyl mine hydrochloride tt cks the cid deriv
tive in nucleophilic substitution re ction. During the form tion of hydroxyl m
ine, KOH is dded to consume HCl so the re ction will not proceed b ckw rd. Duri
ng ferric hydrox m te complex form tion, the solution is cidified by HCl to pre
vent the excess b se from re cting with FeCl3 ( Lewis Acid). A distinct burgund
y or m gent color of the ferric hydrox m te complex is
positive test, d rk
brown solution is uncert in while
yellow solution me ns neg tive. RCOOH deriv
tives, esters, cid nhydrides nd ryl/ cyl h lides would give positive results
. Prim ry nd second ry nitro compounds, imides, some mides, most nitriles, nd
ldehydes with no lph hydrogens give positive test. When n ester, like ethy
l cet te, is re cted with hydrox mic cid, it produces n lcohol.
A dry test tube should be used bec use N met l is highly re ctive with w ter n
d m y ignite violently due to the H2 g s produced. 3. Why is the Luc s test not
used for lchols cont ining more th n eight c rbon toms? The Luc s test pplies
only to lcohols soluble in Luc s re gent (monofunction l lcohols with less th
n 6 c rbons nd some polyfunction l lcohols). Long ch ins of c rbon m ke the c
ompound nonpol r nd the OH group less function l. This results to the insolubili
ty of the lcohol in the re gent, rendering the test ineffective. 4. Expl in why
the order of re ctivity of the lcohols tow rd Luc ss re gent is 3>2>1? The re ctio
n of lcohols with Luc s re gent is nucleophilic substitution re ction. In n
S-n1 re ction, the r te determining step is the c rboc tion. The c rboc tion is
most st ble in terti ry lcohol nd is therefore formed f ster th n second r
y nd prim ry c rboc tion. 5. Illustr te with equ tions the re ctions of the f
ollowing lcohols with Pot ssium Dichrom te. Proof th t dichrom te is strong o
xidizing re gent in n cidic soln: (0 = 1.33 V) (0 = 0.13 V) nbutylalcohol (oxidiz
d to aldhyd/carboxylic acid)
Whn an acid anhydrid, lik actic anhydrid, is ractd with hydroxamic acid,
it producs a carboxylic acid.
For acyl halid,
scbutylalcohol (oxidizd to kton) For amid, trtbutylalcohol (cannot b ox
idizd bcaus trtiary alcohols do not hav a hydrogn atom attachd to a carbo
n)
VII. Guid Qustions & Answrs 1. What proprty of alcohol is dmonstratd in th
 raction with Na mtal? What is th formula of th gas libratd? Th alcohol
xhibits acidic proprty in th raction with Na mtal. Th hydrogn atom is rp
lacd by Na producing H2 shown in th raction: 2 ROH + 2 Na 2 RO( )Na( ) + H2 2. D
ry tst tub should b usd in th raction btwn th alcohols and Na mtal. W
hy? Chmistry 31.1, Qualitativ Analysis
+
6. What functional group is rsponsibl for th obsrvd rsult in Millons tst?
Phnol intracts with nitric acid, nitratd phnol racts with mrcury and mrcu
ry salts ar formd. This raction accounts for th obsrvd rsult in Millons t
st. 7. Why is th Schiffs tst considrd a gnral tst for aldhyds? Pag 11 o
f 13

Diffrntiation of aldhyds from ktons bcoms th main purpos of using Schi
ffs tst sinc it cannot distinguish on kind of aldhyd from anothr. 8. Why is
it disadvantagous to us a strong acid catalyst in th raction of aldhyd or
kton with 2,4DNPH? Th us of a strong acid rvrss th squnc of th ra
ction. Instad of th nuclophil attacking th substrat followd by th lctr
ophil, in th prsnc of a strong acid, th wakr nuclophil attacks th car
bon to stabiliz th forming hmiactal. Watr abstracts th H+ of th hmiacta
l. Hmiactals ar lss stabl and will form actals which do not show th visib
l changs xpctd of th tst.
12. What tst will you us to diffrntiat ach of th following pairs? Giv al
so th visibl rsult. a. actaldhyd and acton Schiffs tst raction with ac
taldhyd will rsult to a purpl solution. Acton on th othr hand will not r
act. Tollns tst actaldhyd will form a silvr mirror. Acton on th othr h
and will not hav any raction. b. actaldhyd and bnzaldhyd Bisulfit tst
will diffrntiat an aliphatic aldhyd from an aromatic aldhyd. Aldhyd wil
l ract fastr than bnzaldhyd. Both will form a rd prcipitat du to cuprou
s oxid. 13. A colorlss liquid has a bp of 199201C and burns with a smoky flam
. Th sodium fusion tst provd ngativ for th prsnc of halogns, nitrogn,
and sulfur. It was not solubl in watr, 5% aquous sodium hydroxid, or 5% hyd
rochloric acid. Howvr, it was dissolvd in sulfuric acid with volution of ha
t. It did not giv a prcipitat with 2,4DNPH solution and did not dcoloriz b
rominmthyln chlorid solution. Th unknown liquid did giv a positiv hydrox
amat tst and was found to hav a saponification quivalnt of 136. Idntify th
 unknown liquid. Smoky flam indicats that th compound is aromatic. It tstd
ngativ for 2,4DNPH, tlling us that it is nithr an aldhyd nor a kton.
A ngativ tst for bromin in mthyln chlorid solution also indicats that i
t is nithr an alcohol nor a phnol. A positiv tst for hydroxamat tst tlls
us that it is an acid drivativ, which can undrgo saponificationthrfor it i
s an str. Finally, an aromatic str with a boiling point rang o of 199201 C
is mthyl bnzoat. VIII. Conclusions & Rcommndations Thr ar many tsts wh
ich can b conductd in ordr to diffrntiat organic compounds from on anoth
r. Som tsts ar also abl to diffrntiat primary, scondary and trtiary ds
ignatd carbon atoms. Th functional groups, th numbr of carbon atoms prsnt,
th dgr of (un)saturation, th ractivity of th compounds to crtain ragn
ts at crtain conditions, and th prsnc of lctronwithdrawing or donating
9. Show th mchanism for th raction of actaldhyd with th following ragn
ts: a. 2,4DNPH
b. NaHSO3
10. What structural fatur in a compound is rquird for a positiv iodoform t
st? Will thanol giv a positiv iodoform tst? Why or why not? Ktons and alco
hols with a mthyl group dirctly adjacnt to a carbonyl group or a carbon atom
baring a hydroxyl group ract with an alkalin solution of iodin to produc a
yllow solid, iodoform. Ethanol will giv a positiv rsult bcaus it can b ox
idizd to an aldhyd with a mthyl group attachd to a carbonyl group. 11. Show
th mchanisms for th iodoform raction using actaldhyd as th tst sampl.
Chmistry 31.1, Qualitativ Analysis
Pag 12 of 13

groups ar som of th ssntial factors which mak organic compounds vary from
on anothr.
IX. Rfrncs Shrinr, R., t al. (1956). Th systmatic idntification of orga
nic compounds. Nw York: John Wily & Sons, Inc. Fisr, L., & Williamson, K. (1
992). Organic xprimnts. MassachusttsL D.C. Halth and Company. Robrts, R.,
t al. (1985). Modrn xprimntal organic chmistry. Nw York: CBS Collg Publ
ishing. Hydrolysis of organic compounds. Rtrivd from: http://www.avogadro.co.
uk/organic/hydrolys is/hydrolysis.htm Tsts for aldhyds and ktons. In Onlin
lab manual hom. Rtrivd from http://www.wllsly.du/Chmistry/chm2 11lab/
Orgo_Lab_Manual/Appndix/Classifi cationTsts/aldhyd_kton.html#Iodofor m Ch
mical Tsts Pag. Rtrivd from: http://www.chmistry.ccsu.du/glagovich/t ach
ing/316/qualanal/tsts/tsts.html Aldhyds and Ktons. In Chmistry coms aliv
. Rtrivd from:http://www.jc.divchd.org/ JCESoft/CCA/CCA5/MAIN/1ORGANIC/OR
G12/MENU.HTM Organic chmistry microscal projction xprimnts. Rtrivd from
: ://www.dmochm.d/proj.htm
I hrby crtify that I hav givn substantial contribution to this rport. ____
_______________________ Bacarza, Maxin Nicol ___________________________ Guiz
, Abigail Ann A.
Chmistry 31.1, Qualitativ Analysis
Pag 13 of 13