Experiment 12 Identification of Alcohols and Phenols

INTRODUCTIONAlcohols and Phenols contain the functional group, OH. In a phenol, the OH group is connected to a car on on a en!ene ring "here as in alcohols, the OH group is connected to a sp# h$ ridi!ed car on ato%. Alcohols are classified as &', (' and #', depending on the nu% er of car on ato%s connected to the car on earing the OH group. Representati)e e*a%ples of a phenol, and three t$pes of alcohols are sho"n elo".

Though these four classes of co%pounds contain the functional group OH, the uni+ue differences in their reaction che%istr$ allo"s one to easil$ differentiate one fro% the other. Phenols are %ore acidic than alcohols. Alcohols as "ell as phenols find a )ariet$ of industrial, phar%aceutical, and e)en household applications. Deri)ati)es of alcohols and phenols are found in %edicines, alcohols are used as co%%on industrial sol)ents etc. Ferric Chloride test: Alcohols are readil$ differentiated fro% phenols using this test. Addition of a drop or t"o of ferric chloride solution to a sa%ple of phenol ,#-- drops. "ill produce a distinct )iolet/purple coloration. Alcohols do not produce such deep coloration "hen treated "ith ferric chloride solution.

0ucas test, chro%ic acid test, and oiling points can e used to differentiate pri%ar$, secondar$ and tertiar$ alcohols. Phenols do not react under the reaction conditions of 0ucas test and/or chro%ic acid test. Lucas Test: A solution of !inc chloride in concentrated h$drochloric acid is called the 0ucas Reagent. The rate of reaction of an alcohol "ith HCl in presence of 1nCl( is dependant on the nature of the alcohol, i.e. "hether the alcohol is a pri%ar$ alcohol, secondar$, and or a tertiar$ alcohol in nature. Tertiar$ alcohols react al%ost instantaneousl$ to gi)e "ater insolu le al2$l chlorides as products ,re%e% er the fact that alcohols are "ater solu le due to H- onding.. R3OH 4 HCl ZnCl R3Cl 4 H(O
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6o if a cloud$ dispersion or as a separate la$er "ithin the solution occurs i%%ediatel$ upon %i*ing the alcohol "ith the reagents then that alcohol %ust e a tertiar$ one. 6econdar$ alcohols "ill for% cloud$ products upon standing "hile pri%ar$ alcohols need to e heated "ith the reagents efore the reaction can occur. This +ualitati)e test can e used to identif$ a pri%ar$ alcohol fro% secondar$ and tertiar$ alcohols. Chromic Acid Test: Potassiu% dichro%ate, 7(Cr(O5 in a+. acid and 8ones Reagent ,CrO# in acetone and sulfuric acid. are t"o co%%on o*idi!ing agents. In oth these reagents, Cr is present as Cr ,9I. "hich is red orange in color. Ho"e)er after the o*idation reaction, Cr ,9I. gets reduced to Cr,III. "hich is dar2 green in color. This color change is e*ploited and used for the detection of alcohol in reath of suspected into*icated dri)ers using a :reath anal$!er. O*idation of alcohols using potassiu% dichro%ate and acid can e used as a %ethod to differentiate tertiar$ alcohols fro% pri%ar$ and secondar$ alcohols. :oth pri%ar$ as "ell as secondar$ alcohols are o*idi!ed using these reagents, producing a green Cr III precipitate. Tertiar$ alcohols are not o*idi!ed "ith these reagents. PURP !E" &. To use the che%ical characteristics to differentiate phenols and the three t$pes of alcohols (. To learn characteristic che%ical reactions of alcohols and phenols PRELA#" Consider the structures of the )arious alcohols and phenols sho"n and co%plete the ta le on the report sheet $ noting the e*pected outco%e of the indicated reactions.

PR CE$URE" Lucus Test: &. O tain the si* un2no"n co%pounds. (. 0a el 5 clean dr$ test tu es "ith the un2no"n nu% ers. #. Add ; drops of each sa%ple to the appropriate test tu e. -. Add & %0 of 0ucas reagent. CAUTION< The 0ucas Reagent is highl$ corrosi)e to s2in, e$es, and other od$ tissue. 6afet$ glasses and aprons %ust e "orn throughout &'=

this test. Clean spills i%%ediatel$. Rinse "ith plent$ of tap "ater if the reagent contacts the s2in. ;. >i* $ tapping the test tu e "ith a finger. If there is no cloudiness % i* $ stoppering and %entl& sha2ing the test tu es. 0oo2 for cloudiness that %a$ e de)eloping during this ti%e. Note $our o ser)ations. If there is no cloudiness after &' %inutes at roo% te%perature, "ar% the test tu es that are clear in a "ater ath ,?@' C. for &; %inutes. Record $our o ser)ations. @. At the conclusion of this test, rinse the contents of the test tu e do"n the drain "ith plent$ of tap "ater. Do not re%o)e safet$ glasses until the rinsing is co%plete.

Chromic Acid Test: :ord"ell-Aell%an Test &. Place into separate clean, dr$ test tu es la eled as efore ; drops of each sa%ple to e tested. (. Add to each test tu e &' drops of reagent grade acetone and ( drops of the chro%ic acid reagent. #. Place the test tu es in a "ater ath %aintained ? ;' C. Note the coloration efore and after heating. Record $our o ser)ations. Ferric Chloride Test: &. Place into separate clean, dr$ test tu es la eled as efore ; drops of each sa%ple to e tested. (. Add to each test tu e ( drops of ferric chloride solution. Note the coloration efore and after the addition of the reagent. Record $our o ser)ations. #oilin% Point $etermination: &. 6et up the apparatus as sho"n in the diagra%. A piece of fire-resistant "ire gau!e "ith a s%all hole is placed on a ring. A test tu e containing a out ( %0 of the alcohol to e tested and a oiling stone is supported $ a cla%p so that the otto% of the test tu e rests directl$ o)er the hole. The gau!e shields the outer "all of the test tu e fro% the heat of the urner, 2eeping it cool enough to cause condensation of the alcohol )apor created upon heating. 0o"er a ther%o%eter ,capa le of %easuring to at least &;' C. until the ul is '.;-&.' c% a o)e the surface of the li+uid. Center the ther%o%eter $ adBusting the ther%o%eter cla%p so that the ul does not contact the inner "alls of the test tu e. (. AdBust $our urner to a )er$ lo" fla%e and %anipulate it eneath the hole in the gau!e until a gentle oiling of the li+uid ta2es place. ,Centle oiling is essential for the success of this deter%ination. 9iolent oiling "ill result in a rapid loss of the sa%ple and possi l$ increase the danger of its eco%ing ignited $ the urner fla%e. CAUTION< If fire occurs, re%o)e the urner and e*tinguish the fla%e $ lo"ing across the opening of the test tu e. 0et it urn out if it doesnDt lo" out..

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Experiment 12 F Report 6heet Na%e GGGGGGGGGGGGGGGGGG Identification of Alcohols and Phenols

A : C D H I C H I 8 7 $ATA TA#LE" Un2no"n 0ucas Test Nu% er Results

Chro%ic Acid Test Results

Ierric Chloride Test

Alcohol Categor$ ,&', (', #', or phenol.

:oiling Point

& ( # ; @ 5
C )CLU!I )! JUH6TION6 &. Iind the section of pages in the Handbook of Chemistry and Physics that "ould help in $our identification if the a o)e ta le of possi ilities "as not gi)en. (. Is it necessar$ to perfor% the 0ucas Test in order to deter%ine the un2no"nsK H*plain.

#. Co%pare the oiling points of the co%pounds "ith three car ons onded aliphaticall$ co%pared to four car ons onded aliphaticall$. Arite a general state%ent of the effect of chain length on oiling point. H*plain "h$ this trend %a2es sense using $our 2no"ledge of 0ondon Dispersion Iorces.

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-. Co%pare $our predicted oiling point for alcohols "ith the h$dro*$l groups on the end as opposed to in the %iddle of co%pound. Arite a general state%ent of the effect of chain ranching on oiling point. Ahat %ust happen to the 0ondon Dispersion Iorces as ranching increasesK

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The oiling points of aliphatic iso%er of phenol range fro% &('- &;= oC. Arite a general state%ent of the effect of the c$clical shape of h$drocar ons on their oiling points. :ased on $our data, are 0ondon Dispersion Iorces greater in a c$clic co%pound or an aliphatic co%poundK

I$E)TIFICATI ) F U)0) 1)! Hach un2no"n is one of the alcohols in the chart elo". Iirst, use the na%e of the alcohol to s2etch the structural for%ula. Ne*t, deter%ine fro% the structural for%ula if the alcohol is a pri%ar$, secondar$, or tertiar$ alcohol. Iinall$, use the oiling point, 0ucas test L Chro%ic Acid test data fro% $our un2no"ns to deter%ine the identities of the un2no"ns. alcohol &- utanol oiling point &&=oC structural for%ula alcohol categor$ un2no"n nu% er

(- utanol

&'' oC

(-%eth$l-(-propanol ,tert- ut$l alcohol. #-%eth$l-l- utanol ,isoa%$l alcohol or isopent$l alcohol. &-propanol (-propanol

=# oC

&#' oC

E= oC =( oC

phenol

&=& oC

&&(