POST I3B DISCTJSSION

fi.tEM 2L(ACT +7)

ACT 4: PURiFICATION BY EXTRACTION
r-ht"t,lc')
- white crystal-like residue t-^lc;-
- benzoic acid

Questions:
1. extraciion - a purification rnethod usd when a substance partitions itsetf
between immisciblb liquids

Basis: a) hffi Dlstribution Law

An organic compound distributes itself between two immisciblb
solvents so that.the ratio sf its.concentrdion in dilute solutions of to
sofuents is constant regardless of the actualconcentration in either
solvent.
b) distributionlpartition coefficient (lq) - ratio of the.concentration of the
solute in the 2 solvents at equilibrium

G in one solvent'
(o'=
C in other solvent

2. Methyl alcohol and ethyl atcohol are pr extratdion solvents bersuse they are miscibte in
water

Choise of a solvent:
a. should be sparingly.soluble in the solvent of the solution
b. should be separated easily frcm thesclute
c. should not react chemically with the solute in an undesirable way
d. should extract little or none of the impurities or other substances present
. e. has a f;avonable lQ , thus readily dissolves thesubstane ts be extmcted
f. non-toxic organic compound with BP < 1OO0C
g- has a BP lower than that of the extracted compound
e.g- CHCI3, CSz, CClr, benzene (CeHr), ether
)

3. Disadvantages of using ether as extracting solvent:

a. volatile b. flammable

4. Stopper be removed from a separatory funnelwhenever a liquid is being drained from a

stopcock:
a. To allowthe entry of airwhich would help in the smooth/uniform drainage of the
liquid through the stopmck
b. to release the pressure formed in the separatory funnel produced by shaking

Uses of separatory funnel:

a- for thorough mixing of liquids b. for separation

v
 ACT. S:PURIFICATION BY RECRYSTAT-L|ZATIO|.t -
1. powderform; whitein cslor
,r/. irEFr..{ a.ceta'1104. - A,.tu | -rr7 tr*

Questions:
sV.-aa l- lo"r'tl8
:
- 6aolzc v1--

RECRYSTALTIZATION- is a purification technique employed when an impure substance is

dissolved in asuitablesolvent ad crystallized again asa pure suhstane.

. Piinciple: Solubility - is the amount sf solid which will dissolve in a given

amount of solvent to give.a saturated solution.at specified temperature

. Basis: differcnces in solubilities sf a solid and an impurity in a given

solvent

1. Bgcrysldlizdion proces+would not give a yield of 100o/o

/-> deufiee! -[\- fr.5r };.s.,^.- vtr^1it^V
b* t__€q -r3 c,f
a. crystallizatioh is not complete 0 cftLr.srat 41r Y^-"^.ol lat
b. loss of solute due to transfer from apparatus 6 another d
c. loss of crystals due to evaporation - - r.r' .7 c*u {r}
2. Crystallization be induced : (2'.T1. t" .5 up'f'rc o el
a. vigorous stining A- 's.ai<]. r. 1\ -
b. 1.1{i Fr r ot
I r L- G.
* Fi, lt/'. :- f<
ice bath
c. seeding - g--'nll tVb' 19 a-a dco( {" c\ s -,i4

2 It is important to minimit* *ulio.Jfti"irnfi nnrffi,ili a not$lutiofr'?Eb

a. to avoid crystallization in the funnel
b. rapid crystallization will occur if there is rnaximum evaporation

Properties of activated charcoalas a adsorbing agent:

a. large surface area
b. porous

5. Chamcterstics of solvent used for recrystallization:

a. should not reactwith the substance to be dissolved
b. should be relatively safe to handle(not poisonous or flammable)
c. should dissofue an appreciable amount of the substance to be purified when hot
and should crysiallize mosit of the substance when cold
d. should not dissolve the impurities readily or it rnay dissolve these to small extenl
only or it should dissolve the impurities readily but not the desired substance
e. could yield wellformed crystals of the desired substance
f. should be capable of easy removalfrom the filtered crystals and therefore its
boiling point should be preferably w/in 60 - 100 oC
 ACT 6: PURIFICATION BY MICROSCALE SUBLIMATION

1. SUBLIMATION- is a process by which a solid is converted direc;tly to vapor without

passing through the liquid state.

o Basis: relatively high vapor pressure of a solid

2. prefened over crystallization in small scale operation

a. a method of obtaining a prodrlct of high punty
b. best adapted 1o use with small amounts of matedal
c. less time and less transfening operation
d. little loss of matefial in the process

3. Applications:
a. when a smallquantity of the solid is used
b. when the solid has a relatively high wpor pressure at temperature belory its
melting point
c. when mmpounds display chanac{eristic property of condensing the solid state

d il[H1i'31T$i*T:11*?3:g';Kurethanthe puriried

go{-.e -T.' fr,c {WpXu;l ra^t-T.,r.e

lft'/
ACTZ: fpApERCHROMATOOnnpHV - r-.6\ar[- fo".c<:-" - l1,v,ty c-rrfsen"nd^<otvPa
l*f t'w'to'V
1. \- significance of & values:
g "' ft"
lTF. used in identifnation purpo$es
- b. -used to greater
determine the afiinity of the solute to the solvent
Rr , greater afrnity of solute to the solvent

2. Basis: dffierential migratbn, that is, migration of components of a mlxture through a

stationary phase

3. Application s of chromatography:
a. for qualitative analysis - determination of components not the amount
b. separalion and identification purpces
c. determination of birclogical and pharmaceutical materials
d. it permits the simultaneous compadson under identical separation conditions of a
series of samples with appropriate reference standards

4. a. CHROIvIATOGRAPHY - Greek uords: chroma - color, graphein - to write

- is a separation technique which utilizes the differential countercrrnent
distribution of the components of a mixture betureen a mobile phase and a
stationary phase
,el} dY Ft"-d b. development the process of allowing the scilvent to more along the
Y.att. oF
^ f ut\cl*Cc oF at S ltaT U11
f+''tver.|'
stationary phase
ut ,Jr*1-. naa- lrcrTel'cl h*.
c. sOlvent flont the maximum distanoe traveted by a solvent through the
dsorbent o-4g-v b on,f ct^rr,a^et)" t,e
A",r*.-f .r4(l tr*."g - Flr* frf
I OLr..v-c-r*,1

F\r-u [3 t,l a
v- wi"" 0-
td-'n...,
\>
 i6. stationary phase - fixed @mponent

e- chromatogram - the arangement of zones resulting from a

chromatognaphic separation; the pattem formed in
the adsorbent rnedium by layers of components
separated by chromatography

t. adsorbent a material such s activated charcoalwhich adsorption can

occurs

g. mohile phase - moving component; liquld

h. & - rate of flout the ratio of the distance the substance moves,
compared with the distance reacfred by the solvent, both rneasured
from point of application of the sample

TYPE MOBILE PHASE $TATIONANVIPHASE, 4?

l."adsorption non-polar or organic solvents silica gel. charcoal, polyamide
2. ion-exchange bufrered aqueous solution ion-exchange resins
3.,partition mixed aqueous organic solvents cellulose, silica gel
4,'lhin layer a liquid a finely divided solid
DBTERMINATION OF PHYSICAL CONSTANTS:

A. IMPORTANCE:
I. Criteria for purity
*pure substance: system of molecules which upon exhaustive fractionation fails
to yield fractions with different properties
2. For identification purposes

B. METHODS OF DETERMINING SPECIFIC GRAWTY:

l. Mohr Balance: devised by Karl F. Mohr
2. Pycnometer Method
*pycnometer a small glass bottle with a ground glass stopper through which a
-
hole is bored
- the bottle is weighed empty, then full of water, then full of the given liquid
3. Ilareos Method: devised by Robert Hare
- measures specific gravity by balancing the pressure caused by a column of a
given liquid against the equal pressure caused by a column of water
4. Use of the Hydrometer
*for rapid rneasurement ofthe approximate specific gravity of a liquid
*hydrometer has a long stem with Hg at its lower end to make it float upright in
-
the liquid being measured; graduations in the stem indicate the value of the
specific gravity

C. OTHf,R PITYSICAL CONSTANTS:

i. Refraction - refers to the change in direction of a light ray passing from one medium to
another of different density, as from air to water or glass.
2. Optical Rotation - is the change of direction of the plane of polarized light to either right
or left as it passes through a molecule containing an asymmetric C.
3. --Density - is the mass of a substance per unit volume.
4. * Conductivity - is the properry of a substance or mixture to transfer heat or electricity; it
is the reciprocal of resistivity.
5. Surface Tension - is the attractive force exerted by molecules below the surface of the
liquid upon those atthe surface air interface.
6. - Specific Heat - is the amount of heat required to raise the temperature of a substance by
1Co.
7. \Avogadro's Number - is the number of particles in one mole of a substance.
8. - Atomic Mass Unit (Dalton) - is exactly t/12 of the mass of a t'C atom; a particular
isotope.
9. Molar Mass oi Gram-Formula Weight - is the mass of a mole of an ionic compound, in
grams, and numerically equal to the formula weight.
POST t3B DlscussloN(cHEM 2L)
ACTIVITY S 11

ACT 9: ALKANES:
Genera Formula - CnHa'€
General Reac*ian - substitution reaction
e.g.
Halogenation reaction : CnHar*z + Xz + CnHz,*rX + HX

Other Name: - PARAFFIN: parum arffinis - " sliglrt affinff'--

Combustion - blue or non-iuminous flame; products: COz + HaO
. ?C.Ha*z + (3n+1)O2 ---+ ZnCOa + 2(n+1)H2O
The relative inertness: due to the strong covalent or sigma bonds b/n C atoms
Sources: naturalgas and Petroleum

1- Physicalstate:liquid

. lfi-tffirr*:F bssdense

^.
L
the one exposed to direct sunlight tumed oolodess wfrile the one placed in the
ocker didn't change color

. CeHro + Brz frv. CeHrsBr + HBr

, --t
./
substitution reaction
t
3. - formation of 2 layers

4' : +
:3:rljll'?no,- 1zco2 i4H2o

QUESTIONS:

1- Equations in the progressive bromination sf methane:

. Bromination- occurs in the presence of light; + result = decolorized solution
UV
r RCHg + Brz ---+ RCHaBT + HBr

Cru + Brz -+ CHsBr + HBr

CHeBr + Bre -> CH2Br2+ HBr
CH2Br2 + Brz -+ CHBr3 + HBr
CHBrs + Brz -+ CBk + HBr

2. PhotoaMivation - an activity invdving the redion of ligtrtto suHances producing a

chemicalchange.
 3. methane - results from the decay of organic matte[ found in coalmines,impt
constituent of a coalgas
ethane - found in natural gas and as a by ptodud in cracking of petroleum
used as a fuel
propane - a fuel gas and chemicalfeed stock
butane - refining petroleum distributed as a fuel {gas,cigarettelighter)
pentane - found in petroleum

4.

1- Preparation:
' A
;,:::-;:-"-
',, R-R + Nax
,

e.g. ZCHrBr + ZNa + Cl+r0ru + ZNaBr

B. By Grignard synthesis

R-CH7X +Mg + R-CHrMgrX

R-CH2-M9X + HzO +R-CHe + HGIttlg-X
e.g. CHarCHz-Elr + Mg -+ CHg,CHrttig-.Br
CHrCHrltJlg-Br + HzO +CH3CH3+ HGMg-Br

ACTIO: ALKENES
ALKENES: GeneralFormula - CnHz'
Geneal Reaction - addition
reaction
e.g. Halogenation reaction : CHz=CH2 + Xz ) CHTCHI
tl
XX
Othername -
OLEFINS -"oilf
Combustion - yellow,sootyflame;COz + HzO +C
Readivi$: due to the presence of double bond ( 1 weak pi bond)

1.
- Physicalstate:liquid
- coloc colorless
- odor: ini&ating
- solubility in watec insoluble
- density comparcd to water: less dense
2. - mixture turned colorless

Brz -+
0. Og;
3. - the solution decolorized and a brown precipitate was formd

0 + 2KMno+ + 4H2o ...+

0:: . zKoH

4. - luminous flame , yellow flame with soot

- alkene - yellow flame with soot; allcane - blue flame without soot
combustion of the alkene:

2CsHro+ 9O2 -+ 4CA2 + 10HzO + 8G

QUESTIONS:

1. Two tests for unsaturation:

A. Baeyels reaction: addition of dilute KMnO+ ( KMnOq + HzO )
permanganate ion and is
[i',ffioJ:TJffi $f:ffi1:rororthe
3-C=G +ZKMnOe +4HzO+ s-GC- +2KOH +2MnOz
lt
OHOH .

(diol)

3. use of
ffi*15ffi:brominein
ccL

-C=C - + Brz -r -C-C-

tt
Br Br

2. Chemicaltests to differentiate an alkene from an allcane:

a. Flame test:
Alkane - blue flame
Alkene - yellow flame with soot
b. Baeyer's test
Alkane - gives a negative resuft
Alkene - gives a positiqresult wtictr is the decolorization of solution

3. alkenesandoccunence ofeach:
a. ethene - notable natural souroe of dhylene is known in coal gas and in
wood gas
b. propene:, from cracked petroleum
c. butene - vapor of isopropyl alcohol
4. Preparation af alkene:

Dehydrogenation method: removal of hydrogen

' not easily accomplished underodinary laboratory conditions
General Method: dehydration of alcshols {R'OH }
- dehydrating agents: conc. HsPO+,eONCllzSOs,PaOs,AlaO"
rlii r ,

a. Dehydration of alcohols:
tto'
RCHrcHzoH R-cH=cHz + HoH
l-fzso+
e.g. CHTCHTOH + CHz=CHz + H2O

b. dehalogenationofalkylhalides:

R-CH-CH-R + 7n -> R-CH-CH-R + TnBrz

Br Br
ACT11: ALKYNES 1:--.
'
' '' 1+;= i'r. -1. l)-\ i: ' 'r "
rr
ALKYNES: GeneralFormula -CnHz.z
General reac-tion - addition reaction :. .-. r\
X X \\' T

e-9. Halogenation reaction: HC=CH + X2 + HC

ll- CH
lt
XX
Combustion -
yellow, sooty flame; COz +
HaO + C
A.8- Lab Preparation: CaQ +
zr-{';o +
Czl-{z Ga(OH)z +
B. Properti'es:

1. Physicalproperties:
A- gas, @lorlesss, odorless wlren purc
B. Chemicat slightly soluble in rlnater, tighterthan air, forms highly
explosive mlxtures with air. Caution must be obervd when it is studied in the
laboratory.

2. Flammability: yellow,sooty flame

2CzHz + 3Oz -+ 2CA2 + ZHzO +2C

3. Reaction with bromine

Turned coloress, it decolorized readily

Br Br

H-C;C-H + 2Br2 +
lt
H-C-C-F|
ll
Br Br
 Alkane- least reacfive (nothing happned)
-
Alkene more readive (decolorized)
-
Alkyne most reactive (decolodzed)

4. .
Baeye/s test for unsaturatrion

oHo
3H-C=C-H + 2KMnOr + 4H2O -+ SH-6- (-n + 2KOH+2MnOzJ
H
(aldol)
5. a.
- formation of red-brown precipitate
- H-C=GH + 2Nl-l+OH + ZCuGl Cu-C=GCu + 2NFLCI + H2O

b.
- formation of white precipitate I

- H-C=C-H + 2N|-LOH + AgNOs Ag.c=GAg + 2Nl-l+NOs +ZHzO

QUESTIONS:

1. Uses of acetylene:
1.
for automobile headlights
2.
as fuel for orryacetylene welding talches
2. terminal alkyne

3. acetylide fiormation is used as test to distinguish between alkene and alkyne

5. Melhods of preparing alkynes:

1. elimination readion of dihalides

a- H-C= C-Ha RCI-hBr + + RCH2g= g1-1
b- R -C= C - Na + RCHzBT -+ RCH2C= CR

2. treating dihalide with boiling potash

, RCHX - CHXR' + KOH + R-C=C-R'+ ZKBr +2HzO

-r ',-:' . ,
-;;
\i . 't ' '-"----- - 'n:':'a' , -- -.--
'"" ,
,...,,"' :-
' t t ',;'^
___--
' --
a' .. t.-, :! : i'-. I '
)r' '. ;."'"' . l-
tu Pfq4*calFroperties:
t. are rwmptar mhrcr$s
2. ilrmluble irn nrartsr h.rt sklble in ether, edlyl alrcfml ard frC!","
3. lem dermm thnn wamr
I

ts" Snurses: i ceal &nr olM ffinki$rn

{:. Ctwrudcal tupperlies: Gs'reral nmaetiolr * substitutiom

1" |-L[L(}6H[WATIOtr; srMtlom of t-t S hatogen

@ + nra 3 @*o HBr

2" FRTfrDEL*CRAFTSAI"JTYI-ATTCIN

@.R*x*'@n+HX
3. TUTTRATTOffi

@ + Firrt& -* ffiru& + rtorl

b- p diredsrs m - diredws

r.i amyr O*' L. Nirru ff)*u

2. athrmryl Z. Carboxyt
@**. @mon
i,tr-"

FICTTVITY ng$.r 13: pnrnarcuH FR0Dtlgrs

rh. Defir$tlsn of tenrw;
,ti
1. Octane no. * ia nwnber whi$ rdens b the relative antit<nock gnOerry d a fi*d
rcfeflr m fts mrnpnrimn vr{Sl a rnh*rre of isoechne and n*leptarrc

sftraigfitcftain allanm- low CI.dane rutiqg

$ehJrdM ring W HC* inftsrnxediale orsne nating
ht$dy bratffied alkarre & arornatic HC - high octarm ratirp
$ilso[irw * a mlffi,re cf al| tlms€ tyfre$ sf HCs hlerded in ffle propormen
, nffi tn girre ffie d€rfrred rxffim raUrlg.
2.
'

F|ashpCIirt - tne mrrnperffire.$ whlch naporizes sufficiendy to fiornr a

mbdure wtth ain tlffi mn be ignited and continue b srryport
{CIstrtnffirt
B. i
i :

i Catomsrnoleurte (t)
* f0O- - shtr4
lrko. of Bp range t.lses
L. petrioH.rm effrffifl -j C6 Cr
to Z0 dry deanrrru
L. grmdire , -l GrCI Cu 30 - 200 rnomi ruil
, lt, kerpsene -i Cr:@ C$ wS- 275 frrd
4t. para-ffin ucw - melts 52* 57 trdle
ffi
Cm

$ASOLI[.{E: kwriln as pem in ffiUhnd, pef,nrleurn tryrlrocartron ftrc| rffid Nrnari}f b punrer
is$Hrnal ernhMfon ergdnm

o prodrdion: a' *s**onffi**ffilH#il;l#ffi'ff#m-"'

h" cablytic rac*ing - oil is fed in a s$eam of sfteanr inb a rffiion
rlem| mufiaining catalYut
I
Kf;${O$fit\lE; a"k.a puryafiFn oil or mal oil ; liguld HC originally wed m ful*s for lannpe and norro
ffied m a hedirq frrc| especially in dornestic heating stenis

s pmdLrtiofli: fradisnd di$lllatipn of pefroleunn

tJlG : mntnins abo*.rti8096 ndnrn, 109& etfrane anrJ the remainirg 1096 !s a mixture of
Hgl"mr allcansi

c l

prCIdr.dlori : ba&rial demy of plant and marine organlwrxs mat fralre becofiE hJrtd
.Mr
the earth? surface
 '': i I l

ACffiVITY Ho" 14: t@elt mrnpour*

A. mnpstleg: ii .

L" Phym;icall
a, terye rmried odors
b, nmct alS halffi are liWids and are heavier than wabr
c. rnoetase insoluble in w&r
d. rn[scibld$ubk in orgnnhc sofuenb - ether, benzene, eflryl almM
?-" Ournrtd fuperties:
a" aonrbuSib,llity: non menbustible
b" frydrotltsb:' I

a.l txsngla bffi ( alldine tndnolnrs)

'

pe$ ( KOH + etrryl alcohol)

b.n tlsingiahofnlk
' R-4 + K0fl -r allcene+lO(+F|OH
l

kepamtiunt i

a. hdqgerson d an dkarw
dkane +)fu*r R-X+hlx

l',
b. redixr befrrcn sr alcohol and hydrorcid
ROll + lX -r $( + Fmfl
,

'i
c. r€affirln b$til,B€n alaohol and phosdpfom trihalide
ROl"l + PXs'-+ 3nD( +
i
Hr[Or
i

d" reaction beturewr alolrol and tfiionyd ddoride

t
ROll SOCb --r RX + $02 + l-l()l

lbille alff halides ard Snrir uses:

t. CCl4 - used for ey deaning
2" 0{Cl3 - gdod sofuert for deaning and degreasing work
3" CFfi3 - Cidrfectant
4. DDT * O$rnroddrenynn*loroeffune- lnsecticide
5. Freur - mflfurodm**ry- - mndensable gas in ooling sysilenu
I
 ,9t'

,"od-

ACIIWTY NO" 15: IODbTORF{

A. Lnborahry FrqfarAnon:

cl.tso(I-t, -n lst, + 4tud.)ft ** fttcoohta + * +

ct-t.[3 3rual 3ftot{
!

Tests for ttue preserm d indine

1. Beils$in test * rriolet mlor of flame
:

2" Sifuer nitrah test - yellor ppt fonned

3" ,addiUofr of ffi{ - purse colomtion- iodine

,' i r horirn or red qbration - indicates brsmine
l

3" alpha halogerdnon ; hdoifnrn tS

]hffibCIf dronlcal M knovvn as iodofiorm test- pcstire testfor
immpour# that onbin nnthvf carbonyl group anO unycompourds
yleld this group u6rn oxidation.
, 1*tlct,
TERPIS;
:

I' RffiyshllizatFron - a pro{rrss wtrerein iodoform crysfials are dissotved in etharnl ard are
tryffilliled again as pure icdoform cryseab
2. Reflts cordeil*r - used b frcat mixtures af sub#nces wittrout tfre hss of nnre
volatile mmponent and to absorb heat of rmparization

Caharlatirg 96 yi,reld:
1" to deermirrc the amount of product
,Z
to dffirrnlne the lam in the activtttr
3.
b ES aCIcuracy of erperiment
ql
$ t{},r --ij -Lli
- "-tt3
S. '(
6i

c{-i1 i-L- bkl

1

;u
I

ooo \
 POST LAB DISCUSSION
CHEM 2L (ACTTVTTY 16 -181

ACTIVITY 16:PRODUCTION AND PROPERTIES OF ETFfYL ALCOHOL:

A. FERMENTATION OF CANE SUGAR

Equation forthe hydrolysis sf cane sugar
C12HzO11 + H?O invertase. C6H12O6 + C*lrzOo
sugar ---------1 glume fruefose

Equation fsrthefennentatbn of the simph sugarto akohd:

C6H12O6 zvmese . zCftCl-bOH + zCOz
- fo-r#ti6n stuYh@e{ipitats
Ca(OH)r + COz --* CaCOs + H2S

B. pnopenles:
1- combustibility - ethanol bumswtth nsn-lur*inousfiame
2' r*-ruff.fficnpri,c sutfate became white in cotor
- ethans{ still conteins water as ii restores ths blue cslor of heated CuSOacrystals
3. tdofarm test fcr etfte*d - forms ydlcw pgt. (CHI3 - lod+form )
CH3CruOH + 4lz + 6NaOH -+ CHle.l" + HCOONa +sNat + SHaO

' 1. Ferme*tatian
- chemical transformation cf organic sub#anes into simpler compounds by the action of
enzyms or organic catalysts poduced by miuoorganisrns under contrclled condition in the
absence of air-

2- Role of yeast - to prwide the enzymes wtricfr are essential forfermentation

a. invertase -
responsibb forthe hydralysis sf dissecr*rarides ( sucrase) to
simple sugars (hexoses).
b. z:fmase -
responsible forthe demmposilion cf a hexose to ethanol and
COz
- role of disodium ptrosphate (NazHPO+) -
to prwirle Ere essential nutr*ents like
minerals and nitrogelr-sourws forthe groring yeast cdb so that they in tum can prwide the
needed enzyrnes for Gnnentation.

C. Efiecfs of aloohd: ALCOHOL - not a stimulant but a depressant

a- long-term etfects:
1. serious physical and mentaldisrderc; life span is usually 10 to 12yrs. shorter
than that of non- ahohcdics.
2. [ntdrferev*ith the absorption and starege af athervitami*s; mi*erals are lost
through inseased urination
3, Cirfiosis {cancer } of the liver
' 4. Cancerc sf the rrlcuth, tftroat and lary*x
5. Some brain cells die, prcducing menr!ry lass, wnfusicn & leaming difficulties
b. short-term efie*:.
1. the drinkels judgment ard thinking becorne du*ed
2- intoxicatien - dumsy movemects, sluned speecfr & difculty in maintaining
balance
D. Degree Proof - is equal to twice the prcent by volume cf an skoholic drink
,qCrMTY 17: PROPERTTE$ AND REACTTONS OF ALCOHOLS

Alcohols: -OH {readirre slte or site ndrere c-lrenrical reaciion occura and the C hoHing this group)

Aliphatic R-OH
Amrnaltis ApOH

Monohydrorylor Monohyddc: 1 -OH

FolyhydroxylorPolyhydric: 2s> -OH

Pdmary Ahohol:
at ha$t 2 H atoms on the C atom bearing the -OH group
Secondary A&oohof only 1 H on the OH-beadng group C
Tertiary Alcohd:
no H atonr on the Ol-Fbearing group

A. PhysicalProperties:
1" BP - for normd almhols (strai'ght- chain), the BP's increase regulady urith MWs.
For branched-almhols, the more bnancfies, the lowerthe BF.
2. MP - genemlly, alaohols have very lw Mp.
3. H-bonding -
form of sttracdion b/n partially positlve H and the lone petrs of an atom.
4- Occunene at roonr temperature:
C5 : fluid {colorless lhuids)
Ce- Crr : oily onsistency
C12 - 6bove : solids
5. solubilily in water : Cr - Cs - comple{ely scfruble
Ce - G+ - deqeasing Subility
B. ChernlcalProperties:
1" Acidity and Basidty
- alffihds are acidic and bsic as water (amphoteric). The acidity is due due to
less elec*runegative H thd can be easily given to a base. The basicfu is due to
the more electronegative CI that cqrld eaSly affipt prston.

2. Readions of Abhols

A. Solubility in H20: increased --OH . increased solubility

alcohol cold water hotuater 5%NaOH

ethvl acohol miscible miscible miscibte
benzylalmhol immiscible immiscit*e immiscible
qlvmrol miscible miscibb miscible

B. Viscosity: increasod -OH, inseased visor*ty

alcohol result
ethvlakohr* 7 sec
benzyl ahohol 1O sec
glYcerol Tmin&9sec
- glyrercl
C. Reac{ion with Na: reflacemenl d H by Na to form ALKOXDE

rt
?-C-OH + 2Na --+ 2-C-O-Na +l-lzt

alcohol result
ethvl alcohol bubbk rere brmed
benarlalcohol bubbles rrere fiormed
glverol bubbles wge fiormed

Equations:
a. ZCH3CruOH + 2Na 2 Cl-lgGl-le:G.Na + Hal

b. Z + 2Na --+ 2 a Hzl

@nzOn C-CHzGNa
3. zQHrQl-t-9H2 + 6Na -) z9ru-qH - gH, + 3HzT
Ou OH dn O-rua b-tta Gt'ta
D. oxklation (addition of acidihed KaCraQ)
primary (1o) alcohol:
R-CH2-OH + KzCraOz + l'lzSOr -+ RCOOH +Crz{SO*)s +KaSOr+ H2O

sscondary (21 abohol:

R-9H-OH + ltOrzor + HaSOr -r Rp=Q + Crz(SOrla + IGSO* + HeO
KR
T t' abohol --+ NO REACTTON
alcohol colorchanoes observed
ethvl alcohol dark sreen
benzvlalcohol dark oreen
Ethylene slycol dark orcen

Equations:
a. SCl-faSHrOH + zj{zOlrfi:' + SFlzSOr -r 3C|'bGOOH + 2Gr2(SOo}" + KzSO+ + 11HzO
b. 3 ()ICHTOH + zKzCr"o7 + 8H2SOa-+ 3 +ZCr2(SOr)s + KrSOo + 1 lHeO
@COOH
c. t$il;rffi + ZKvCr&t+ SHzSOr + 3COOH 4OOH + 2CrlSOft + KzSO+ + 1 lHzO
E. EsteriFrcation (Formeilion of esters)

RCOOH + ROH --+ RCO'OR + HOH

1. - pbstk balkron odor
CHTGHzOH + CH3GOOH -* C|'bCOOCF|24H3 + HzO

2. - the odor rcsembles that of nail polistt

dH2oH + cn=.8cr -- '+3+c@ + Hcr

3. - fruity odor

CHrCH-CHz *cH.8c | --+ Cl{#OOQru + HGI

0n 6n 6n crucoocFb
cH3coocru
QUESTIONS:

1. Monohydnory dohds are morc reac{ive than polyhydrcry almhols because there is no
crowding qf OH

Uses:

a- nethyl abohol ftyood ahohol) - itwasor(lindlyobtained bythedestruc{ive

distillatbn of $rood chips in the absene dcin today, most rn€ilhanol is
synthelzed by catalytic pntoe*s in whk*r C0 and Flz gas rcaci to brm methanol

CO + 2Ht -> CHgOH

" 1. nunutaciure of paints, vamishes
2- converted toformaldehyde, a ctembd us€d to make plasths

b. effiyl alcolrol (grain alcohol)- oHained fiotn the fermentation d sugars

and starches ftom many different sources ( grains such as @m, $ilreat, rye &
barley); the abholic solution that rcsults from the fermentation contains only 12-
15 % ahhol! because yeast celb cannd survive hQhermncentnalions.

f. industrial solvent & for preparatbn of tincture

?- sohrentfor chemical reac{bns. @uers, vamishes& stains
3, prefn of cfiemicals used as detergents,llavodngs & frqranm
. 4. soporifp-slep producing
c. isoplopyl alcohol (rubbing alcoho[ - is nrde by catady{h hydrdlon of propylene
cHscH=cH2 + HOH --+ CHrgH4Fr"

1. antiseptic;disinfeciant
2. intermediate for the prepamtion of estere and dher industrial chemicals

d. ethylene gty€ol

1. gincipal ingredient of certain antlreezes

2- as hydraulic brake fluid

e. glycerol{glycefine}

f . its ability to absorb rrtater makes il vduable hunreciant (moisturizing agent)

fortoM and fioods
2. emoilient (sorftening agent) fior skin mrdilrtrners
3. manuftaciure of dynamites, paper making inks, hydraulic bnake fruids
4- rcH suppositodes
ACTIVITY 18:CHEMICAL TESTS FCR ALCOHOL AND PHENCLIC COMPCUNDS

Color Tests for specific alcohols:

A. Tests for MethylAlcohol
1. Salicylic acid test -
methyl alcohol with salicylic agd and conc.HzSO+give a
peppermint odor due to form'n of methyl salicylate or oil of wintergreen.
peppermint dor
esterification:

@i* + cruoH + @;1""" +HoH

2. Resorcinol test - an indired test for me{hand

- oxidation of mednndto formaldehyde
2Cu aOz + ZCuO

- CUO + CHgOH -+ HCHO + Cu + HOH

- formafion of a purple/ vndet color at the junction befireen the reorcinol and HzSO+

B. Tests for Ethyl alcohol

t. lodoform test - yellow ppt for compourds conkining methg
carbonylgrcup, CH3CO
CH3OH - no
CH3CH2OH - yes
CH3COCH3- yes
CH3CH2CH:OH - no
C|{gQHOH - yes
cru
- initrating odorlyelbw prccipilate

2. Ethyl acetate tesf -reac{ion b/n acetk acid and ethyl atcohol to give e*hyl acetate
{plastic balloon odor) and water

CH3COOH + CHgCHSH -+ Cl-leCOOCFliCHs + H2O

C. DIFFERENTIATION OF 10, * , 3O ALCOHOL

1. Lucas test. Lucas rgt lmL of HCI + lml otTnCb - differene is based on rate of
formdion of alkyl halides

almhol immdediately upon after standing for afrer standing for 30

standino 5mins mins
n- alcohol dear ctear formation of 2 lavers
sec-butvl alcohol dear formation of 2 lavers
tert-butyl alcohol formalion of 2
lavers

30 reacis fastest, 20, 10

 2. oxidation Rate test. 1o' 20, 30

retes of rear*ion odor mlar

(1*.2d. 3d )
n-butyl alcohol 1* iniiatinc gree*ish bhck
sec-buM alachol
tert-butvl alcohol
r.lfit
initatinc
initatina
c ree*ish Hackf lic hterl
remains omnge{no chanqe}

a. cHecH3cHrcH2oH Y** cftcH2cFtzcHo Y crucH2cFtzcooH

HeSOu

to]
b. CH3CH2QHOH
c. 30
cru redion
alcohol - no
-> CH:CF{zC=O
-Cru

D. Tesi for glycerol:

Acralein test - speeiFc for glycerot whk* inv*es its d*hydratbn apn hetr'ng it with
potassium bisulfate lo produae an unsaturaied aHehyde, pn:penal {acralein) , with a

-*"'H11##:**
2-propenal
l{2s04
?H' - QH - E+
----> cHz= cHCHC + zFlzc
\( t'{ s$
E. Test for phenolic compounds; phenol or carbol'rc add
1- Fenic cfibriele test- given by phenoEie mmpcunds with a frce ortfto position and
those lvftlch do not conlain eledron-withdrawing groups
- produffi a vioH coloration
2. Millon's test: given by phenolic compourds and is a specific test for the amino
add, tyrceine
produm a red eloration

Structurd Chemicalnatrp 2 important uses

farmula
Phencil QH carbalic acid -antise$ic, manuMure of
o synthetic fihrs

salicylic 2-hdroxybenzoic acid -antipyretic, prcparation of

acid @*3'?* drugs

resorcinol

picric acid
ffi -OH
&hydrcrypherx*

2,4,Strinitrcphenol
-tanning, antiseptb

-man ufdure of explosive

o+r {6}
\l-No,
rvo, Sram staining
ACTTVITY Nc.?rJ : HTtr{FR R*O*R
PROPERTIES;
1. highly votatile ; BP of ether - 36.4 "C { tower compared to the normal body temperature}.
Z. Sotunp in benzene and ethylalcohol but insoluble in water, dil HCland NaOl-lsalution"
-
non polar nature makes it an excellent solvent for many organic cornpouttds
-
good solvent for laboratory extractions
3. less reactive than alcohols,- due to lack of - OH precludes reactions with Na which are
characteristic of alcohols

PREPARATION:
1. Dehydration of akohol
2 CH3CHaOH .*+ CH3CHzOCH?C& + H2O

Z. lMlliarrrson synthesls ( reaction behpeen an aikoxide and an alkyl halide)

R-0-Na + R'-X ----' R-O-R' + NaX
s$f - c(x-o*$d t cJ{rc(r} -t cFrcAr-o*' tl\a$g+NqI
ANSWERS to Questions: t,
- L -o -N^ * ctloc tt. T
cfa

}f., -?-
r
o-cH,L{3 + ti'rf
-
ctt"
ctr.; petroleum ether
i," sulfuric ether
.1
t.
a. composition " diethyl ether pentanee and hexanes
b. solubifity in water insoluble partfafiy
c. odor characteristte cldor faint petrole u m-like odor
d. oxidation slowly oxidized by tha neutral reaction
action of peioxide
e. boiling point 3S.40C 40 * 6fc
3. Ether has wiCe applications in the medicalfield:
a. used as generalanesihetic
b. used as a carminative
c. used to remove adhesive tapes due to tts solvent pct1,\rer
There is a need for precauticn in its use because it is highly volatile and flammable and
explosive when mixed with air.

4, Ether compared to alcohol does not contain H un?ted to 0 and hence cannoi form H
bonds or associated molecules.

5. anesthetic - a substance that reduces sensation of pain in surgery or other medical

procedures: causes physical insensibility

sedative - a drug that has a calming/ tranquiiizing effect; rnost of it produces sleep or
general anesthesia; it rnay lead to severe poisoning when taken excessively

carminative * a drug that relieves flatulence; expeliing gas from the stomach

antiseptic - a substance that is applied to the body to destroy or prevent growth of

bacteria and other microorganisms.

Disinfectant - any sustance used chiefly on inanimate objects to destroy or inhibit growth
of disease- causing microorganisms
POST LAB DISCUSSION
CHEst ZL:ACTIVITY 21

ACT 21: ALDEHYDES

ALDEHYDES: n€-H or RCHO

?
; Aliphatic aldehyde: R - e-H

ex. Formaldehyde: H-t-H

o @8-,
o
RESULTS:
acetaldehyde: CHr- t-H
o8-'
reactions formaldehvde. aela benzaldehvde
with KMnOr rejdish brsurn oot reddish brown npt reddish brown ppt
with Tollen's rqt silver minor silver minor silver minor
with Fehling's rst brick red ppt brick red ppt- brick red ppt
with SchifFs rst magenta red color maqenta red color maqenta red color
with NaOH formation of oi[ fonnation of oily formation of oily
layer layer laver

REACTIONS:
tol
A. OXIDATION: RCHO -, RCOOH
a. with acidified potassium permanganate: reddish - brown ppt., MnO2

b. with Tcllen's reagent {ammoniacal AgNO3} - silver mirror test

c. with Fehling's reagent: brick-red ppt; CuzO

with Schiffs reagent

- Schiffs reagent (para-rosaniline hydrochloride) is
fuchsin dye decolorized by SOz gas. Because of
some molecular rearrangements , aldehydes restore
the maqenta red color of the dye.
B. POLYMERIZATION REACTION: + NaOH

a. Cannizarro's reaction - this occurs only to aldehydes w/c do not contain H

atoms**t-S:i:,ffil1""'T,?-"Jli-?rrpropanar,benzardehyde

oo
_H + +
2H_C NaOH -+ H_d_O_Na CHg_OH
ao
r54-* + NaOH -NA +OCH-
Z
-,rAf d-O-tta + ACHr-OH

b.
V
Aldol condensation -
V
this occurs to aldehydes containing an active H
attached to C next to the carbonyl C

p9
2 CHg -c -H OH- CH3- ,CH - CHz - c -n
oFt
acetaldehyde aldol

C. ADDITION REACTION: + NaHSOg ) (

- white preciipitaJs

D. MILK TEST:
- purple ring \
^l , [O *\ {*^*&\Ac
- test for formaldehyde in milk as a preservative ( 1 part HCHO/10,000
parts)
formaldehyde is commercially sold as FORMALIN ( 40% HCHO in
aqueous soln)

*
QUESTIONS:
1. SPECIAL REACTIONS OF FORMALDEHYDE:

a. HCHOreacts with ammonia to give hexamethylenetetramine ( used as a

(i) drug, a urinary antiseptic-urotropine ;renders the urine basic; (ii)
preparation of powerful high explosive known as cyclonite, CsHoNoOe)

b. Cannizaro's reaction of HCHO with NaOH

2HCHO + NaOH -+ CHgOH + HCOONa
w$ "\c\'d
 c. formation of formose, a sweet tasting syrup and a mixture of sugars, when
HCHO reacts with calcium hydroxicie
GHCHO -+ CeHrzOo

d. formation of useful resins when HCHO reacts with certain compounds

HCHO +
casein --
karolith
HCHO + phenol --- bakelite
2. Uses of importarrt aldehydes:
a. formalin- used as germicide, fungicide, insecticide and embalming
agent

b. chloral - a hypnotic, in large dose as an anesthetic, can be converted

to chloroform by heating with an alkali

c. urotropine - used as disinfectant for urinary antiseptics

3. Aromatic aldehyde has a stable conjugati..re structure which makes it unreactive

to other compounds , while aliphatic aldehyde reacts faster because they have
open structure

1. Reactions:
a. aldehyde +
RCHO + 2KMnO+ + HzSO+ +RCOOH + KzSO+ + 2Mn0zl + HeO
Ctr\3c\\o { 2 (-\r^Oq + Rasoq -X1c$*{[O" /qrc,oo*
b. aldehyde + Tollen's Rgt(ammoniacalAgNQ3)
RCHQ + 2AgNOr + 2NH+OH *+ RCOOH +2AgJ+ 2NHrNOr + HzO

c. aldehyde + Fehling's Rgt

RCHO + 2CuSO++ 4NaOH -+ RCOOH + CuzOJ + 2Na?SO ++ 2HzO

d. aldehyde + NaOH (Cannizaro's Reaction)

oo
zH-C-u + NaoH +H-6-o=lta + GHs-oH

e. aldehyde + sodium hydrogen sulfite

p NaHSOT gH
n-d-u --+ n*-H
bo.ll"
f . Preparation of aldehyde from primary alcohol
tAgl
2RCH2OH + 02 -> 2RCHO + ZHzA,
9., Linear polymerization of formaldehy.de;
HeO
HCHO -+ HO - (CHzO )- H

h- Cyclic polymerization of formaldehyde:

-CHo
-+ ? -q
fiCHO i.,,;9oq
.u!._ o_c tla
i. Linearpolymerization.bfafutatOetiyde:

OH3CFIO .-+ HO,{CHO}

CHr
-H
* j. Gyctic,polyrnerizatign gf acetaHenyde:
u
3 GHgCHO -+ otc! )'u
il25o4 I I
CH-CzHt
CilHr*-
oo/!
POST l-AB DTSCUSSTON

ACTMITY 22: KETONES

o
KETONE: R
=
b- R' or RCOR
81' $olubility:
ne is sorubre in water, ethyrarcohor and ether

82. Chemical properties of acetone

a. Tollen's Test
- no reaction
b.
;
Fehling's Test

3ttryf*,
- no reaction
d. with NaOH
- no reacfion
e. addition of sodium bisutfite
cloudy white precipitate
9H.
cHr- 8*r. + NaHSo3 4 cHr4-
_ oH
$o.n"
i _
ff8f$HH"ffii:"'
C&COSH3 + 4NaOH + 312-+CHl3 + CH3GOONa + 3Nal + 3l'l20

QUESTIONS:

1. Uses of acetone: ( simplest ketone):

a. solvent for waxes, plastics and lacquers
b. principal solvent for cellulose acetate in preparation of rayon
c. solvent ior nemoving oil and dirt ftom the skin before giving hypodermic
injections
d. for drying hypodermic syringes and glassware (highly volatile and
evaporates quickly)
e- mild antiseptic
2. Preparation of acetone

7. CHe- CH = C -H + Heo, -+ cH.S - CHe

z 2cHr8_o_Ca + cHr_E_cHr+zcace

3. preparalion of ketones from secondary alcohols

oxidation of secondary alcohol, -+ cft$GHg
"*r[il:H
KETOSIS - abnormal irwease of ketone bodies in th-e b,orf as in diabetcs melitus
 POST r.AB DTSCUSSTON
ACT|V|TY 23-24

ACT 23: MONOCARBO)ffLIC ACIDS: RCOH or RCOOH

A. Physical Properties:
1.
S-,n^l,c \ic ,

odor ohvsicalstate xn with litmus

\\ A-w"d
G**"'\ acetic acid initating liquid blue'red - s\-.ger\
Rl"H initatino
1

\ I nrooionic acid liouid blue-red

n \-----
"tg S:uo l stearic acid odorless solid blue-red f lrr^'o"r'^1
benzoic acid odorless solid blue-red **'S
salicylic acid odorless solid blue-red

- odor of aliphatic carboxylic acids of 10 and more C diminish

because of their lack of volatility
- high molecular weight acids are in !he_ setid slate
degree of acidity decreases as the HC chain increases
2.
water ether ethvl alcohol
acetic acid miscible miscible miscible
benzoic acid insoluble soluble soluble
salie:llic acid inssluble soluble soluble

they are sol uble n

i no n-ion izi ng/non:polar/org an ic so_l-ve- nts

B. Chemical Pr:operties:_
--- - --+- - esterificatisn reaction reaetion bln a carboxylie acid and an
-
alcohof -
Rffi''+_ + ROH___+ R€OGRI +_ FtaO
plastieballObn o-dor-
ethyl acetate
HzSO+ O
cr*.8-on + cHacHaoH ---+ CH3C-O- CHzCHe + HzO
a- peppennint odor
methyl salicylate
o
tt

0-o-cH3
A.On
+ CHIOH ---+ \) +Hzo
 2. decar'boxylation {rernoval of carboxyl group} - reaction wl sada
lime

a. it is csmbustible and bums with blue flame

CHTCOONa + NaOH Sgq CH4+ + NazCO:

b. irritating odor
cooH

0 + 2NaoH Caq + Nazffie + Hzo

Qt
c- initating odor
s.ooH
+ 2NaoH gg + Nazcor + Hzo
0l*- 0)"t
3. reaction with ferric salts - forms reddish brcnrun ppt
SRCOONa + FeCls --+ Fe{RCOO)s*f + 3?*laCl
3CHgCOONa + FeCls --+ Fe{CHgCOO}gJ + 3NaCl

b- mlor became violet

4. Millon's test -reddish color

- presenee of phenolie group in salieylie acld

ACETIC AC[D: tOI tOl

CHTCHzOH -+ CHcCHO -+ CHcCOOH

CHICHaOH + KMnO+ +H:SO+'* CHTCOOH + MnOe + KzSO+ + HzO

1. used in vinegar in pickling and curing of meats

2. as asuitablesolvent duets its stability
3. mfc. Of rayon, cellulose,acetates, white lead & other important
r*etaflic a€tates
4. mfc- Of valuable synthetic medicinals {aspirin, acetanilide)
BENZOIC ACID

+ KMnor +Hasor-* + Mnoz + Kzso+ + Hzo

6)-cHOH tr$c*H
1. trsed asfmd preservative
2- mfc sf various cosmetics and dyes
3. mfc of Blastics and insect repellants

SALICYLIC ACID

cH"oH /AcooH
oH -+ VltoH

1- used in the goduction of oil of wintergreen

2. production cf aspirin
3. used in shampoos;ointments fsr treatment of dandruff, aene &
skin dis.

Reduction of rnsnocarboxylic acid- forrns an alcohol

LiAIH+
RcooH . -+
ods"oo\ L$.S c(g
RSfikoH
\or\
Gxidatisn of rnsnscarboxylic acid - fonns carban diaxide and water

RCOOH + Oz -> GO2 + 11tg

Cl,se,oot\ tJ0a J *, t ? (e o
ACTTWTY 24: FOR$lllC ACID: HCOOH
Occurrence: in sweat, urine, present in stinging ants, bees, nettles

A. Physical Properties:
1. colerless, pungent liquid, with a BP of 1O1sC
2. miscible in watel almfrol, etherand glyerol
3-' strongest carboxylic-acid
4. -verycotrosive and has a vesimnt {blbtering) action
onthe skin

3. Chemical Properties:
1. -
Tollen's test silver minor
- HCOCH AgNOr +NH+OH -+ H:O + CO: + AgJ. + NHTNOg
+
2. -
Fehling's'test formation of brick-red ppt
- I{COOH + ZCuSO+ + 4NaOH * HzO + GOz+ CuzOI + ZNazSOr

3. Mercuric Chloride test

- formaiion of white pPt
- HCOOH + HgCl2 --* HgzCle + COe + HzO *
4. Demmposition by Sulfuric Acid
- non-luminous flarne

ssrc. HzSO+
- HCOOH' --+ HeO + CO

5. Oxidation
color became dark green, formation of white ppt at the tip of glass rod
- HCOOH + KaCreOr +4HzSO+--* l(eSOr + Cre{SO+}+ 3eOz + THzO

QUESTION$:

1" \Afhat makes formic acid different frorn other monocarboxylic acids?
a. strongest cf all carboxylic acids {t0x stronger than acetic acid)
b. exhibits reducing propertiesdue to its aldehyde group
c. possesses an aldehyde and carboxyl groups
d. pow*rh:l reducing agent
e. can bth be dehydrated and dehydrogenated

- dehydratio;t.

c*na Ha$o+
- HCooH Heo + co
 dehydrogenation:
1600C
- HCOOH -+ CO2 + lf2

2. Methods of preparing formic acid

a, Hydrolysis of hydrogen cyanide

HCN * ZHzQ + HCI -r NH+CI + HCOOH

b. Decomposition of oxalic acid, using glycerol as a catalyst

glyerol
(COOH)z HCOOH + COz + HzO

c. Goldschmidt process: commercial preparation of formic acid

_ 1s0oC HzSO+
CG + NaOH HCOONa HCOOH + NaHSO+
high pressure

d- oxidation of methyl alcohol

Iot
'--+
toj
CHsOH HCHO -+ HCOOH

3. Uses:
a. strong antiseptic action
b. dehairing hides of animals
c. as a reducing agent for metallie ions and dyes
d. in textile, tanning and rubber industries
POST LAB DISCUSSION
ACTIVTTY 2.5'26

ACTIVITY 25: ACETIC ACID

A. OCCURRENCE:
1.vinegar (3-6%):acetic acid is the sour principle of vinegar nasutting frcm the
oxiOition of etiranol present in wine or hard cider under the influence of
bac{eria Mycoderma aceti (mother of vinegar).
2. occurs free in smallamounts in plant juices, meats and perspiration
3. crude pyroligneous *id ( 6%): a by-product in the manufactre of wood
charcoal

B. PREPARATION:
1. alcoholic fermentatiron
2. from wood

C, PHYSICAL PROPERTIES:
1. has sour taste
a colorless liquid with penetrating pungent odor
glacial acetic acid is a little less than 99.406 acgtic acid (glacial "L. glacies, ice";
because it solidlfies to an ice like mass at 16.60C

a. Tolten's test: no silver minor

b. Fehling's tesf no reac*ion

: HilTx"-"JlglXlfi;il[,f,iff,'+"nen's, Fehrinss and Mercudc

chloride tests but negatively with acetic acid .
no

2. formation of reddish brown precipitate

3CHaCOOH + FeCb +3NaOH + Fe(CftCOO)g +3NaCl + 3H2o
a. plastic ballmn odor c$4
CftCOOH + CHaCH:OH -* CH3COqCru + HzO

' 3 : :ffixTlg,:"rdisris
- pigment in paints
- ?CHgCOOH + ZCu + Oe --+ Cu(CHsCOOlz.Cu(OH)z

--.UV
{^,fl\n$
V
, llq?
A1 \
'€
)il4 \\&
&Kr
III. QUESTIONSJ

1. Preparation of acetic acid by Grignard synthesis

CO, H*
R-Mg- X --' R-COOMgX -+ RCOOH + Mg*2 + X
COz H*
CHyMg- Cl --+ CHTCOO-Mg- Cl -* CHTCOOH

2. uses of aoetic acid:

a. used in the manufrcture of photographicfilms
b. used as intermediate for producfion of vinylacetate
c. important chemicalin paint and adhesives industry
d. as condiment
e. manuf;acture of dyes

v3. HG,
Complete chlorination of acetic acid

S3;*?x,".iU;1;tU*ttt
+
L\c\r,,.,o$,* cL-n h{s*'*
IUPAC: trichloroethanoic acid r\ cl
Uses: used as askingent and for removing warts :
Li "t *rr;og *Sct
I
ACTIVITY 26: OXALIC ACID: (COOH)2 or HaCzOr or COOH
cooH c(

A.
1. PhysicalProperties:
Physical$ate: solid solubility in water: soluble
Color white solubility I alcohol: soluble
Odor: odorless solubility in ether: insoluble
- sublimes at 150 to 't60oC
- efflorcsces slowly in air and becomes anhydrous at 1000C

2. irritating odor
' - (COOH)2 --' HCOOH + COz

3. formation of white precipitate

- (COOH)2 + CaClz + 2NHTOH CaCzOr + 2NHaCl + ZHzO
4 formation of white precipitate on glass rod with limewater
H25O*
a. (COOH)2 ---) GO + COz + HzO
b. 2CO 1 Or -' 2QQz
c. COz + Ca(OH)z -) CaCOs + tnrO v

5. no reaclion
- not a good reducing agent
- (COOH)2 + AgNO3 + NHaOH --+ no reaciion
 violet color disappearcd
reducing property
S(COOH)z + 3HzSO+ + 2KMnO+ + KzSO+ + 2MnSO+-\'10CO2 + SHzO

flammable
fomation of whiG prcciPitate
HCOONa --' GOONa a Hz
Cootta
2Hz + Oz-
COOrua + CaClz --+ CaCOr +frrlaCl
booru"

Iil. QUESTIONS:
1. Preparation of oxalicacid:
a. Gay-Lussac'scommercialmethod:
HzSOr
2HCOONa (COONab + Hz
(COONa)a + (COOH)2 +NazSOr
b. preparation by Scheele in 1776 ( oxidation of sucrose with nitric acid)
c',,il,'gn +-12HNos -* (cooHb + 12No + 11H2o
c. hydrolysis of cyanogen
HOr-l/HCl
(CNh ---) (COOH)2 + NILCI

2. Uses:
a. as an acid rinse in laundries
b. as a bleach, as a laboratory reagent, in dyeing, and calico printing
c. used in the prepardion of dyes, in photography, and in cleaning of
metals
3. csF ruPAc coMMoN"rtrnr-rre
(COOH), ethanedioic acid o:calic acid
UOOC-CH"-COOH 1,3-propanadioicacid malonicacid
HOOG(Cruh-COOH 1,4-butanedloicacid suminicacid
nOgejCHtr -COOH l,spentanedioicacid glutaric acid
Hoo+icnrli -Coon 1,&hexanedioic acid adipic acid
HOOGiCHts-COOH 1,7-heptanedioicacid pimelicacid
ACT|V|TY 28
ACID HALIDES AND ACID ANHYDRIDES

I. CHEMTCAL PROPERTIES:
A. Reaction with water (hydrolysis)
1. - blue litmus tunrs to red; an acid
RCOCI + HOH -+ RCOOH + HCI
CHgCOCI + HOH -+ CHgCOOH + HCI
it is hot

2 : I?Ii'Ilxi,ff"'01Tn'1 +HNor
3. - blue litmus paper turns to red, it is cold y'arr,.1g nIu.
(RCO)zO +HOH +
RCOOH + RCOOH

'04
cH3$ o C cH, * HoH -+ 2cHrcooH
, l- no reaction
- CHgCOOH + AgNO3 ---+ no reaction
B. - plastic balloon odor

Reaction with alcohol {alcoholysis)

RCOCI +ROH+RCOOR+HCl
CHTCOCI + CH3CHaOH -+ CH3COOCH2CH3 + HCI

2' - plastic balloon odor "*\"r"'\i''St 4 *\ .-^\'o\

(RCO)2O + ROH -+ RCOOR + RCOOH
-CHsCOOCOCH3 + CHaCHzOH -+ CHTCOOCHzCHa + CHTCOOH

C- Reaction with aniline

1. - forms brown ppt

RCOCI + CoHsNHe -+ RCONHCcHs + HCI

CH:COCI + CsHsNH2 ) CHsCONHCoHs + HCI

2. - formation of brown pptlzlayers

(RCO)2O + C6HgNH2 ) RCONHCoHg + RCOOH

CH3COOCOCHT + CoHsNHz -+ CHTCONHCoHs + CHTCOOH

0r
t+\ttot\cu3
00
 D. Reaction with NaOH
1. - formation of 2 layers
(RCO)aO + NaOH -+ RCOONa + RCOOH
CH3COOCOCHa + NaOH --+ CHaCOONa + CH3COOH

RCOCI +
NaOH -+ RCOOH + NaCl
+
CH3COCI NaOH +CH3COOH +NaCl

ilt.
($rtsttl"co1"A'lS3
QUESTIONS:
1. Preparation of acidJ derivatives: grr'c$a((*tt*\
r.\r ^e,$,'((atp
* {c\3't
a. acid haride
RCOOH + plb
eg. CH3CH2COOH + PCI + CH3CHaCOCI + H3PO3 - f"S-'
tt\3coo{( Qc\r ..+ Ct\jCo s\*$3qgq
RCOOH + SOGIz -+ RCOCI + SOa + llCl
' 69. CHTCHzCOOH + SOCIz -+ CHgCHzCOCI + SOz + HCI

RCOOH + HX -++ HOH

RCOX
eg. CHgCHzCOOH + HEr -+ CHsCHaCOBT + HOH
b, acid anhydrides
RCOOH + R'COOI{ -> ( RCO )2O + HOH
eg. CHgCHzCOOH + CHsCHzCOOH -+ CH3CHzCOCCHzCH3 + HOH
oo
RCOOH R'COCI =+ ( RCO)2O + HCI
+
eg, CH:CHzCOOH + CHTCHaCOCI + (RCOlzO + HCI

RCOOH + RCONH? --) (RCO)2 + NH:

CHgCHzCOOH + CHgCHzCONHz -+ (CH:CHzCO}zO + NHs

c. acid amides
RCOOH + NHr -)
RCONHz + HOH
eg. CHaCHzCOOH +
NHs + CHsCHzCONHz + HOH

RCOOH + 2NHs --+ RCONHz + NH,4OH

eg. CHgCHzCOOH + 2NHr -+ CHTCHzCONHz + NH+OH

2, acetyl chloride and acetic anhydride are more preferred as acetylating agents
because they show great reactivity and produce irreversible reactions in the
preparation of other acid derivatives. They can serve as intermediates in the
conversion of the less reactive carboxylic acids to more reactive classes of
compounds
I
order of reactivity of acid derivative
acid halide> acid anhydride > ester > acid amide > carboxylate

* acetylating agents: often react at room temperature

-
are very reactive chemically
-
are easily prepared

4. Acetanilide:

NHCCHg
o
- analgesic and antipyretic
- used in the synthesis of sulfa drugs

5. AgNOg test can be used to distinguish acetyl chtoride from acetic anhydride.lt is
a test for chloride ions as shown by the formation of white ppt.

/
ACTIVITY 29:ESTERS: RCOR' or RCOOR'
' Preparation:

1. carboxylic acid + alcohol: RCOOH + ROH -+ RGOOR' + HOH

1. acid halide + alcohol
2. acid anhydride + alcohol

A. ASPIRIN: alcohol portion of the salicylic acid reacts with acetic

anhydride

-cooH p9 rAcooH o
-oH + cH.c-o-i-cHg-+ L!il-o-q-cH.
o
+ cHs-d- oH

- the aspirin was dissolved and it produced bubbles

COOH ft"COONa
O-p-CH3 + NaHCos -> \/O-q-Cnr + HzO + COz
b\'b
- aspirin is sold in the form of its sodium salt because it is more
soluble than pure aspirin thus more readily absorbed
{_,_o r i \r .."\ $u r.\

\
1 --S,otrq\', c i,l
,n 'L
B. OIL OF WINTERGREEN; the acid portion of salicylic acid ieacts with alcohol
- peppermintt odor

,ft-cooH
V-oH + cHroH -']!ilo1 ^'i%.n.+ Hzo

*dk+ *\u1\"\t
C. ARTIFICIAL FLAVORS:

1. bananalpear flavor: acetic acid + isoamyl alcohol

CHsCOOH + CHTCHCHzCHzOH -+ CHTCOOCHzCHzCHCH3+ HOH

CHs GHg

2. pineapple flavon butyric acid + ethyl alcohol

C HgC HaC HzCOOH+C H3C l-lzOH+C HrC HzC HzCOOCH2C H3+ HO H

' 3. apple flavor: isovaleric acid

isoamyl alcohol +
CH' '
CH3qHCHzCOOH+CHsCHCHzCHzOH-+CH3QHCHzCOOCHzCHzCHCH. + H2O
CH' CH. .,* an
"1\ tl:"s*rir c
4. rum flavor: formic acid + ethyl alcohol
HCOOH + CHgCHzOH -+ HCOOCHzCHg + HzO

ODORS:
1. plastic balloon. acetic acid + ethyl alcohol
CH3COOH + CHgCH2OH -+CHgCOOCHzCH3 + gtg

2. varnishes and lacquers: acetic acid + amyl alcohol

CH3COOH+CH:CHzCHzCHzCHaOH-+CH:COOCHzCH2CH2CH2CH3+ H2O

3. flowers: acetic acid + methyl alcohol

CH3COOH + CH:OH -+ CH:COOCH: + HOH
nl'\\\ "ttlolt
1. Some impcrtant esters and ester derivatives:
a. aspirin acetyl saiicylic acid
cooH
-oc-cH3
d
- reduces the risk of r€urrence of strake
- used as an antipyretic and analgesic
b. methyi salicylate - oil of wintergreen

coocH3
-oH

: ;:-i':l'n:il.n perrumes and navor

c. salol * phenyl salicylate

COOCoHs
roH

- :: i#,i,t:;ffi133.1;,lJe*cines
2. Preparation of esters:

a. From carborylic acids and alcohol (esterification )

RCOOH + R'OH -+ RCOOR' +'HzO

Ex. GHTCHzCOOH + .GHgOH -+ GHgCHaCOOCHT * Hr9

3. acid halide + alcohol

RCOX + R'OH -+ RCOOR' + HCI
Ex. CHaCOCI + CHrOH -+ CHTCOOCH3 + HCI

3. Definition of terms:
a. analgesic -
drugs that relieve pain without the loss of
@nscrousness
b.. antipyretic:"- a substance that reduces fever
c liniment - a liquid applied to the skin by gentle fiiction for
temporary relief of pain, stiffness and muscular fatigue
d. enterjc coating -
coating for medical preparation
4. Other esters:

a. spermaceti- largely cetyl palmitate; fr:om the hond cavity of sperm

whale

CHg(CHzh+COO(CHz)rsCHc

b. camauba wax -
from Brazilian palm leaves; used as a
component of automobile and floor waxes

c H3(cH2)26coo(cHz)gr cHs

c. - largeiy myricyl palmitate ; from honeycomb cells

leeswax
C H3(C H2)1 +COO(CHz)as0 Hr

(' r-
,' ^*'to\ ltotA -

Ll$ro. * ctr. tr o t ,n, *C* $rort $\rt ot{ .

0r) b

s"f,u{.'." otrrl .i (
9

Oq[rDu
1Y r*1.+'-(Pr x-Y>-*d
\PO

" Ld2*d6,*
\ g, t1g *r.,
is9
l.gU'{tou
.-Av d
" -\Y, XfO-u
"/" 1,r\,1 z \_f'
,. (oo
-
\,2
, \r t:"li