Survey of Chemistry I (CH 131)

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Properties of Carboxylic Acids and Esters

Background Carboxylic acids are structurally like aldehydes a d keto es i that they co tai the carbo yl grou!" Ho#ever$ a im!orta t differe ce is that carboxylic acids co tai a hydroxyl grou! attached to the carbo yl carbo " % &C''H (he carboxylic acid grou! (his combi atio gives the grou! its most im!orta t characteristic) it behaves as a acid" *s a family$ carboxylic acids are #eak acids that io i+e o ly slightly i #ater" *s a,ueous solutio s$ ty!ical carboxylic acids io i+e to the exte t of o ly o e !erce t or less"

-&C''H . H/' 0 -&C''1 . H3'. *t e,uilibrium$ most of the acid is !rese t as u 1io i+ed molecules" 2issociatio co sta ts$ Ka, of carboxylic acids$ #here - is a alkyl grou!$ are 1314 or less" 5ater solubility de!e ds to a large exte t o the si+e of the -1grou!" ' ly a fe# lo#1molecular1#eight acids (u! to four carbo s) are very soluble i #ater" *lthough carboxylic acids are #eak$ they are ca!able of reacti g #ith bases stro ger tha #ater" (hus #hile be +oic acid sho#s limited #ater solubility$ it reacts #ith sodium hydroxide to form the soluble salt sodium be +oate" (Sodium be +oate is a !reservative i soft dri ks") C6H41C''H . 7a'H 0 C6H41C''17a. . H/' 8e +oic acid Sodium be +oate I soluble Soluble Sodium carbo ate$ 7a/C'3$ a d sodium bicarbo ate$ 7aHC'3 $ solutio s ca carboxylic acids also" eutrali+e

Survey of Chemistry I (CH 131)

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(he combi atio of a carboxylic acid a d a alcohol gives a ester) #ater is elimi ated" 9ster formatio is a e,uilibrium !rocess$ cataly+ed by a acid catalyst"

CH3CH/CH/ C''H . CH3CH/'H 0 H/' . CH3CH/CH/ C''CH/CH3 8utyric acid 9thyl alcohol 9thyl butyrate (9ster) 9sterificatio 0 :Hydrolysis (he reactio ty!ically gives 63; to <3; of the maximum yield" (he reactio is a reversible !rocess" * ester reacti g #ith #ater$ givi g the carboxylic acid a d alcohol$ is called hydrolysis; it is acid cataly+ed" (he base1!romoted decom!ositio of esters yields a alcohol a d a salt of the carboxylic acid) this !rocess is called saponification. Sa!o ificatio mea s$ =soa! maki g$> a d the sodium salt of a fatty acid (e"g"$ sodium stearate) is a soa!"

CH3CH/CH/C''CH/CH3 . 7a'H 0 CH3CH/CH/C''17a. . CH3CH/'H Sa!o ificatio 0 * disti ctive differe ce bet#ee carboxylic acids a d esters is i their characteristic odors" Carboxylic acids are oted for their sour$ disagreeable odors" ' the other ha d$ esters have s#eet a d !leasa t odors ofte associated #ith fruits$ a d fruits smell the #ay they do because they co tai esters" (hese com!ou ds are used i the food i dustry as fragra ces a d flavori g age ts" ?or exam!le$ the !utrid odor of ra cid butter is due to the !rese ce of butyric acid$ #hile the odor of !i ea!!le is due to the !rese ce of the ester$ ethyl butyrate" ' ly those carboxylic acids of lo# molecular #eight have odor at room tem!erature" Higher1molecular1#eight carboxylic acids form stro g hydroge bo ds$ are solid$ a d have a lo# va!or !ressure" (hus fe# molecules reach our oses" 9sters$ ho#ever$ do ot form hydroge bo ds amo g themselves) they are li,uid at room tem!erature$ eve #he the molecular #eight is high" (hus they have high va!or !ressure a d ma y molecules ca reach our oses$ !rovidi g odor" Objectives: 1" (o study the !hysical a d chemical !ro!erties of carboxylic acids@ solubility$ acidity$ a d aroma" /" (o !re!are a variety of esters a d ote their odors" 3 (o demo strate sa!o ificatio "

Survey of Chemistry I (CH 131) Procedure Carboxylic Acids and Their Salts Characteristics of acetic acid

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1" Place i to a clea $ dry small test tube (133 x13 mm) / mA of #ater a d 13 dro!s of glacial acetic acid" 7ote its odor by #afti g (movi g your ha d ,uickly over the o!e e d of the test tube) the va!ors to#ard your ose" 'f #hat does it remi d youB /" (ake a glass rod a d di! it i to the solutio " Csi g #ide1ra ge i dicator !a!er (!H 1&1/)$ test the !H of the solutio by touchi g the !H !a!er #ith the #et glass rod" 2etermi e the value of the !H by com!ari g the color of the !H !a!er #ith the chart o the dis!e ser" 3" 7o#$ add / mA of / D 7a'H to the solutio " Cork the test tube a d shar!ly ta! it #ith your fi ger" -emove the cork a d determi e the !H of the solutio as before) if ot basic$ co ti ue to add more base (dro!#ise) u til the solutio is basic" 7ote the odor a d com!are to the odor of the solutio before the additio of base" E" 8y dro!#ise additio of 3 D HCl$ carefully reacidify the solutio from ste! o" 3 (above)) test the solutio as before #ith !H !a!er u til the solutio tests acid" 2oes the origi al odor retur B Characteristics of benzoic acid 1" Fou #ill #eigh out 3"1 g of be +oic acid for sam!le si+e com!ariso " 5ith your micros!atula$ take some sam!le e,uivale t to the !re1#eighed sam!le (a exact ,ua tity is ot im!orta t here)" *dd the solid to a small test tube (133 x 13 mm) alo g #ith / mA of #ater" Is there a y odorB Dix the solutio by shar!ly ta!!i g the test tube #ith your fi ger" Ho# soluble is the be +oic acidB /" 7o# add 1 mA of / D 7a'H to the solutio from ste! o" 1 (above)$ cork$ a d mix by shar!ly ta!!i g the test tube #ith your fi ger" 5hat ha!!e s to the solid be +oic acidB Is there a y odorB 3" 8y dro!1#ise additio of 3 D HCl$ carefully reacidify the solutio from ste! o" / (above)) test as before #ith !H !a!er u til acidic" *s the solutio becomes acidic$ #hat do you observeB Esterification 1" I to five clea $ dry small test tubes (133 x 13 mm)$ add 13 dro!s of li,uid carboxylic acid or 3"1 g of solid carboxylic acid a d 13 dro!s of alcohol accordi g to the scheme i table 7ote the odor of each reacta t" /" *dd 4 dro!s of co ce trated sulfuric acid to each test tube a d mix the co te ts thoroughly

Survey of Chemistry I (CH 131) by shar!ly ta!!i g the test tube #ith your fi ger" Acids and Alco"ols !est tube % 1 / 3 E 4

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Carboxylic acid ?ormic *cetic *cetic *cetic Salicylic

Alco"ol Isobutyl 8e +yl Iso!e tyl 9thyl Dethyl

3" Place the test tubes i a #arm #ater bath at 633C for 14 mi " -emove the test tubes from the #ater bath$ cool$ a d add / mA or #ater to each" 7ote that there is a layer o to! of the #ater i each test tube" 5ith a Pasteur !i!et$ take a fe# dro!s from this to! layer a d !lace o a #atch glass" 7ote the odor" Datch the ester from each test tube #ith o e of the follo#i g odors@ ba a a$ !each$ ras!berry$ ail !olish remover$ a d #i tergree " Saponification !"is part of t"e experi#ent can be done $"ile t"e esterification reactions are being "eated 1" Place i to a large test tube (143 x 1G mm) 13 dro!s of methyl salicylate a d 3"4 mA of 6 D 7a'H" Heat the co te ts i a boili g #ater bath for 33 mi " -ecord o the 2ata Sheet #hat has ha!!e ed to the ester layer (1)" /" Cool the test tube to room tem!erature by !laci g it i a ice #ater bath" 2etermi e the odor of the solutio a d record your observatio o the 2ata Sheet (/)" 3" Carefully add 6 D HC1 to the solutio $ 1 mA at a time$ u til the solutio is acidic" *fter each additio $ mix the co te ts a d test the solutio #ith !H !a!er" 5he the solutio is acidic$ #hat do you observeB 5hat is the ame of the com!ou d formedB * s#er these ,uestio s o

Survey of Chemistry I (CH 131) the 2ata Sheet (3)

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Survey of Chemistry I (CH 131) Esters &ata '"eet 7*D9@ HHHHHHHHHHHHHHHHHHHHHHHHHHH P*-(79-@ HHHHHHHHHHHHHHHHHHHHHHHH

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2*(9@ HHHHHHHHHHHHHH S9C(I'7@ HHHHHHHHHHH

C"aracteristics of Acetic Acid Property 'dor (ater 'olution )aO* 'olution *Cl 'olution

Solubility

!H

C"aracteristics of Ben+oic Acid Property 'dor (ater 'olution )aO* 'olution *Cl 'olution

Solubility

!H

Survey of Chemistry I (CH 131) Esterification (est (ube 1 / 3 E 4 *cid ?ormic *cetic *cetic *cetic Salicylic 'dor *lcohol Isobutyl 8e +yl Iso!e tyl 9thyl Dethyl 'dor 9ster

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'dor

'aponification 1" 5hat has ha!!e ed to the ester layerB

/" 5hat has ha!!e ed to the odor of the esterB

3" 5rite the chemical e,uatio for the sa!o ificatio of methyl salicylate"

E" 5hat forms o reacidificatio of the solutio B 7ame that com!ou d"

Survey of Chemistry I (CH 131)

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Esters Post,lab -uestions 7*D9@ HHHHHHHHHHHHHHHHHHHHHHHHHHH 2*(9@ HHHHHHHHHHHHHH S9C(I'7@ HHHHHHHHHHH

1" Ho# do carboxylic acids a d esters differ i their characteristic odorsB

/" Aook i the Cha!ter Carboxilic acids a d 9sters i your textbook ( or co sult library$ I ter et ) a d fi d@ *) Citric acid is !rese t i HHHHHHHHHH $ malic acid is !rese t i HHHHHHHHHH$ acetic acid is !rese t i HHHHHHHHHH a d lactic acid is !rese t i sour HHHHHHHHHH" 'veruse of muscle tissue results i the buildu! of HHHHHHHHHH acid" (he sti g of a a t is caused by HHHHHHHHH acid" HHHHHHHHHHH acid is a co stitue t of butterfat" S!i ach$ cabbage a d rhubarb co tai HHHHHHHHHH acid i additio to im!orta t vitami s" 8) 5hich esters are res!o sible for the flavor a d odor of@ 1ras!berry 1a!ricot 1!each 1!ear 1a!!le C) *s!iri $ a ester of HHHHHHHHHHHHHH acid #ith HHHHHHHHHHHH acid$ i hibits the sy thesis of a class of hormo es called HHHHHHHHHHHHHHHHHHH$ molecules that cause HHHHHHHH$ HHHHHHHH a d HHHHHHHHHHHHHHHHHHH #he !rese t i the bloodstream i HHHHHHHHHHHHHHHHHHHH levels"

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Esters Pre,lab Assign#ent 7*D9@ HHHHHHHHHHHHHHHHHHHHHHHHHHH 2*(9@ HHHHHHHHHHHHHH S9C(I'7@ HHHHHHHHHHH 1" 5rite the structures of the follo#i g carboxylic acids@ a" *cetic acid b" ?ormic acid c" Salicylic acid /" 5rite the !roducts from the reactio of be +oic acid a d sodium hydroxide"

3" 'ctyl formate has the flavor of ora ges" 7ame the alcohol a d the carboxylic acid eeded to sy thesi+e this ester"

E" 5hat is a soa!B