SOAP This is a favorite exercise of lab manuals.

Many of the ones I've seen use ethanol to aid solution during saponification !hich can be ha"ardous and concentrated salt to precipitate the product !hich is unnecessary. #e use the procedure !e found in a free pamphlet from $e!is %ed &evil !ho ma'e grocery(store lye. )ou start by ma'ing a fairly concentrated sodium hydroxide solution. According to the recipe dissolve *+, g -./ o".0 1aO2 in ...3 $ -/.4 pints0 soft !ater approximately 5 M. In our scaled( do!n prep the student uses ./ m$ of 1aO2 and /5 g of fat. The student !arms the fat in a bea'er set into a larger bea'er containing !ater -a 6double boiler60 to avoid overheating to a temperature appropriate to the fat used. 7or shortening such as 8risco they use +4 degrees9 for lard they use *4 degrees. This procedure also !or's !ith olive oil for !hich heating isn't even necessary. Though the resulting soap is a little soft it holds its shape !ell. They then add the 1aO2 very slo!ly !ith steady stirring using a tongue depressor or popsicle stic'. It ta'es at least ten minutes for the bre! to thic'en up. One drop of food coloring or fragrance is added here and stirring is continued until the stuff piles up !hen dripped bac' into the bea'er. It is then poured or scraped into a small plastic drin'ing cup and left in the dra!er to cure for a !ee'. The !rite(up for this exercise is pretty sub:ective. My general aim is to mesh !ith stuff !e are tal'ing about in lecture so I as'ed them -.0 !hy !e refer to soap as a 6salt6 -/0 !hat 'inds of molecular properties enable substances to dissolve in !ater leading to -*0 their guess as to !hether the glycerol produced is soluble in !ater -apparently not obvious0 and -+0 to sho! the structures of the products expected from saponification of ethyl acetate -!hose structure I give them9 !ith the breadth of material to cover I'm not too intense on nomenclature0.

Preparation of Soap

By Walter Scharf and Charles Malerich Natural Sciences/Chemistry Baruch College New York, NY 10010

Introduction

Soa , from a chemical stand oint, is a salt !or a mi"ture of salts# of fatty acids$ %s with all salts, soa contains a ositi&e ion, usually Na' or (', and a negati&e ion, usually the anions of long)chained car*o"ylic acids o*tained *y the hydrolysis of animal or &egeta*le fats$ +hese fatty acids, of which there are a*out ,0 naturally occurring mem*ers, are car*o"ylic acids containing 1-, 1., or 1/ car*on atoms in an un*ranched chain$ +he e&en num*ered chains result from the fact that fats are synthesi0ed in cells *y the olymeri0ation of a ,)car*on acetate unit$ 1n addition to the normal !straight chain# saturated acids, there occur se&eral with hydro"yl grou s, and/or one or more dou*le *onds in the car*on chain$ the resence of unsaturation !dou*le *onds# in molecules of fatty acids, fats, or sou tend to lower the melting oint of these com ounds and to cause them to *e in the li2uid state at room tem erature$ +hus, &egeta*le fats are relati&ely unsaturated and li2uid under the ordinary conditions, while animal fats, *eing relati&ely more saturated, are solid, or semi)solid, at the same tem erature$ 3or this reason, &egeta*le fats are commonly refereed to as &egeta*le oils$ !We say relati&ely saturated, or unsaturated *ecause *oth &egeta*les oils and animal fats contain saturated and unsaturated chains#$ +he reason why dou*le *onds lower the melting oint of a fatty acid chain, is that the sections of the chain attached to the dou*le *ond are attached cis) wise to each other ! ro*a*ly *ecause the dou*le *ond cis configuration roduces a *ent chain which does not easily adhere to a neigh*oring chain *y a 4an der Waals attraction hence a lower tem erature !lower mo*ility# is re2uired for these molecules to adhere in order to form a solid crystal lattice$ 1t is interesting to note, that straight chained car*o"ylic acids ha&ing an odd num*er of car*on atoms melt lower than e&en chained acids of com ara*le molecular weights$

+he most commonly encountered fatty acids in natural fats are gi&en *elow5

Saturated %cids

6auric %cid !7odecanoic %cid#

C89)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C::8

Myristic %cid !tetraderanoic %cids#

C89)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C::8

;almitic acid !he"adecanoic acid#

C89)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,) C::8

Stearic acid !octadecanoic acid#

C89)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8,) C::8

<nsaturated acids5

:leic acid !octadec)=)enoic acid#

C89)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8>C8) C8,)C8,)C8,)C8,)C8,)C8,)C8,) C::8 6inoleic acid !octadec)=, 1,)dienoic acid#

C89)C8,)C8,)C8,)C8,)C8,)C8,)C8,)C8>C8) C8,)C8,)C8,)C8,)C8,)C8,)C8,) C::8

%ll fats are esters !though, not all esters are necessarily, fat?# of the trihydro"y alcohol, glycerin, and fatty acids$ Since each molecule of fat contains three ester grou s, fats are often referred to as triglycerides to distinguish them from other materials ha&ing a fatty or greasy te"ture, such as wa"es !mono esters of long chain alcohols are car*o"ylic acids# mineral oil, and etroleum @elly !long)chain hydrocar*ons#$

1f A)C::8 re resents a generali0ed fatty acid !A is a hydrocar*on chain of 19, 1B, or 1C car*ons# then, the general formula for a fat is

Note that the fatty)acid residues in a ty ical fat molecule are usually different? 3ats from different sources ha&e different ercentages of the common fatty acids, and can *e distinguished from one another *y a 2uantitati&e analysis of these constituents$ Soa is re ared *y hydroly0ing a fat under alkaline !*asic# conditions$ +he reaction is called sa onification, and roduces one molecule of glycerin and three molecules of soa , for each molecule of fat taken$

+he fats and oils most commonly used in soa re aration are lard and tallow from animal sources, and coconut, alm and oli&e oils from &egeta*le sources$

+allow and lard are the fats se arated from solid *eef fat !suet# and hog fat, *y the rocess of rendering$ Aendering consists of *oiling the animal fat in a ot with an e2ual &olume of water until a layer of melted fat collects on to $ !when the animal tissue is heated, the fat in the cells melts, e" ands, ru tures the cell mem*rane) and then flows out$ Since the fat is immisci*le with water, and has a lower density, it forms a floating layer on the to of the water in the ot$# the rendered fat is then drawn off, and allowed to solidify *y cooling$ +he length of the hydrocar*on chain and the num*er of dou*le *onds in the car*onylic)acid ortion of the fat or oil determine the ro erties of the resulting soa $ 3or e"am le, a salt of a saturated, long)chain acid makes a harder, more insolu*le soa $ Chain length also affects solu*ility$ +allow is the rinci al fatty material used in soa making, with coconut or alm oil *lended in, to roduce a softer !more solu*le# soa which will readily lather$ Soa s made with (:8 !caustic otash# instead of Na:8 !caustic soda# are li2uid rather than solid, at room tem erature$ ! otassium salts ha&e a lower melting oint than sodium salts$# +oilet soa s are generally carefully washed free of any remaining alkali used in the sa onification rocedure to a&oid irritation and drying of the skin$ %s much glycerine as ossi*le is usually left in the soa , and erfumes, coloring, and medicinal agents are sometimes added$ %lso added, are antio"idants to re&ent the soa from turning rancid$ Many soa s are su erfatted, i$e$ not all of the fat is hydrolysed, in order that the final soa ha&e some fat remaining to lu*ricate and smooth dry and sensiti&e skin$ Besides tallow and coconut oil, there are many other natural fats and oils which can *e economically em loyed to make soa s of &arying degrees of 2uality$ +he less ure the raw material is, the more likely the soa will ha&e an off)color !generally yellow or *rown#, and an undesira*le odor$ !im ure fats are sometimes treated with *leaching agents *efore sa onification, *ut this adds to their cost$# D"am les of such other starting materials in soa manufacture are5 coconut oil, alm oil, oli&e oil, cottonseed oil, sesame oil, corn oil, Soya *ean oil, hydrogenated &egeta*le oils, rosin, na hthelinic acids, and greases made from animal skins, *ones, tankage and gar*age$ +he lower grades of soa s are used as yellow laundry soa , soa owders, cleansers, and industrial soa s$

Below is a short glossary of terms em loyed to descri*e s ecial ty es of soa 5

Castile soa )) a mild soa originally made in S ain with ure oli&e oil$ +oday many EcastileF soa s are made with other &egeta*le oils$ Castile is a mar&elous cleanser, roducing a rich lather$

Cream soa s G soa s containing cold cream materials, moisturi0ers and emollients$ Cream soa s are articularly good for dry and delicate skin

7eodorant soa s G soa s to which anti*acterial agents ha&e *een added to reduce odor)causing *acteria$

3loating soa s G soa s ha&ing air *u**les incor orated to lower the density$ +his causes the *ar to float$

8y o)allergenic soa s G Mild formula soa s, low in otential irritants$ +hey usually roduce a oor lather$

Medicated soa s G soa s containing medications such as tar, sul hur, or anti*acterial ingredients, used to treat acne and other skin disorders$ Medicated soa s re2uire through rinsing and are not recommended for sensiti&e skin$

Milled soa s G these are the most commonly used, mass roduced soa s$ Milling refers to the mi"ing of color, erfume and soa flakes$

:atmeal soa G % rough Gte"tured soa to which oatmeal has *een added as a mild a*rasi&e and lather$ Hood for oily, dry, and normal skin$

Procedure

+wo rocedures for soa making are gi&en, a EcoldF and a EhotF rocess$ +he cold rocess, suita*le for homemade soa s, roduces soa *ars which retain the glycreine *y) roduct, and if the amount of alkali em loyed in the sa onification is limited, an e"cess of fat !su erfatted#$ +he hot rocess, more suita*le for la*oratory or industrial re aration, yields a more chemically ure owderI *y) roducts and e"cess starting materials are se arated$

1$ Cold rocess

You must wear goggles or glasses$

When using a thermometer in this e" eriment, ne&er use it to stir li2uids$ 1nstead, use a fire olished glass rod$ to ro erly measure the tem erature of a li2uid, hold the thermometer so that its *ul* is sus ended in the center of the li2uid while reading the mercury le&el$ 1f the li2uid is *eing heated on a hot late, do not the thermometer *ul* to rest on the *ottom of the container, as it will then *e o&erheated$ Aemo&e the thermometer from the container after each reading$ Note5 the thermometer su lied does not re2uire shaking down *efore or after reading$ ;lug in a hot late and set to high$ Weigh a 1B0 ml *eaker on the tri scale and add /g of Na:8 ellets to it$ 8andle Na:8 with care as Na:8 can *urn the skin and is es ecially harmful to the eyes$ 1n the hood, add ,B ml of cold water to the *eaker$ Stir the mi"ture of Na:8 ellets and water, until a clear solution results$ Caution5 the *eaker will *ecome &ery hot as the Na:8 dissol&es$ Weigh a ,B0ml *eaker on the tri )scale and add B/g of fat !Crisco &egeta*le shortening works well# to it$ +hen lace the *eaker on the hot late with low heat and with occasional stirring, melt the fat to melt com letely$ Warm the melted fat to *etween -0)B0 oC$ Aemo&e the fat from

the hot late and add the lye solution to the fat with stirring$ Stir the fat and Na:8 mi"ture continuously and until an emulsion is formed$ Your mi"ture should look like a thick, light yellow milk shake and should stay emulsified !should not se arate into a fat and Na:8 layer#$ 1f your emulsion se arates, the fat is too hot and needs to cool$ 6et the mi"ture cool on the *ench to with occasional stirring until an emulsion, which does not se arate, is formed$ You may want to add erfume or other additi&es at this oint$ ;our the emulsion into a lastic cu and lace in your drawer for the reaction to run !it takes a*out ,- hours for the reaction to *e com lete#$ +ake the soa home with you and let age for a*out two weeks$ 7uring this time a owdery layer of NaC:9 !soda ash# will form on the surface, as residual Na:8 reacts with C:, in the air while the soa is drying$ +his owdery layer should *e sliced off and the soa is ready to *e used$

11$ 8ot rocess

You M<S+ wear goggles or glasses?

;lug in a hot late and set it on 81H8$ 8alf fill a -00 ml *eaker with hot water from the sink and lace on the hot late$ When the water *egins to *oil, ad@ust the heat, so that the water *oils gently, *ut continuously$ While waiting for the water to *oil, weigh a ,B0ml Drlenmeyer flask on a tri le *eam *alance and add 10g of fat !Crisco, s ry, or lard# to it$ 1n a 1B0ml *eaker re are 100 ml of a B0)B0 solution of alcohol)water, *y mi"ing B0 ml of water and B0 ml of =BJ ethanol or methanol$ Weigh another 1B0 ml *eaker on the tri le *eam *alance, and add 10g of Na:8 ellets to the *eaker$ 8andle Na:8 with care as Na:8 can *urn the skin and is es ecially harmful to the eyes$ 1n the hood, mi" the Na:8 with 9. ml of the of the B0) B0 alcohol)water solution to it$ Stir the mi"ture until a trans arent solution is formed$ Caution5 the *eaker will get &ery hot as the lye dissol&es$ ;our the lye solution into the Drlenmeyer flask containing the fat and mi" well using a stirring rod or *y swirling with a *eaker tongs$ Clam the Drlenmeyer in the *oiling)water *ath and with occasional stirring, allow it to cook for at least 90 minutes$ While the mi"ture *oils, some foam will form !due to soa formation#$ +ry to minimi0e e"cessi&e foaming, *y adding small adding small ortions of your alcohol)water solution$ +he reaction is com lete when oil glo*ules are no longer &isi*le when the reaction mi"ture is stirred$ 8alf fill a .00 ml *eaker with 900 ml of clear !filtered# saturated salt !NaC1# solution and B0 ml of water$ ;our the still hot reaction mi"ture containing soa , glycerine, e"cess Na:8, and alcohol into the salt solution$ Stir the resulting mi"ture and allow to stand for B)10 minutes$ +he soa will collect as a white layer on the surface of the salt water in the *eaker$ ;re are a suction tra from the &acuum flask, which will *e used later to filter the soa re aration$ Bend a long iece of glass tu*ing into a right angle !instructor will demonstrate#, and ush one leg of the *end through a one)hole ru**er sto er fitted for the mouth of the flask$ When inserted, the glass tu*e should e"tend to a*out K inch from the *ottom of the flask$ +he e" osed leg of the *end should *e cut off at a*out 9 inches from the *end, and, *y means of a iece of ru**er connector tu*ing, *e attached to a 1,)

inch length of glass tu*ing$ +he side)arm of the &acuum flask is now connected to the &acuum outlet with ressure tu*ing$ When the suction is turned on, this de&ice will act like a &acuum cleaner, sucking u li2uid instead of dust$ Be sure the suction is :33, *efore roceeding$ Bring the *eaker containing the soa re aration ne"t to the suction tra , and lace the Es outF of the tra into the *eaker ha&ing it touch the *ottom$ Slowly turn on the suction, and watch the *ottom !a2ueous# layer *eing drawn into the &acuum flask$ 7raw off most, *ut not all, of the *ottom layer$ Be ready to sto the suction instantly, if it a ears that some of the soa crystals are *eing sucked u $ You can sto the suction 2uickly *y ulling the ressure tu*ing away from the outlet, then turning off the &acuum$ Caution5 %t no time should the &acuum flask *e allowed to fill more than half)the tra , and our out its contents$

When most of the a2ueous layer in the *eaker has *een drawn off, filter the remaining mi"ture of soa and li2uid through a Buchner funnel !with filter a er attached # to the suction flask$ Wash the crystals on the filter with B ml ortions of ice)cold water$ ;ress out any remaining moisture from the cake of filtered crystals on the funnel with the flat end of a clean cork, or the clean *ottom of a small *eaker$ %llow the roduct to suck dry for 10)1B minutes$

+urn off the suction, detach the Buchner funnel, and with the hel of a clean s atula, transfer the soa crystals to a large sheet of smooth a er$ ;ick u the sheet and slide the cystals into a clean, dry 1B0 ml *eaker$ 6ea&e the *eaker stand, unco&ered in your drawer for se&eral days to air)dry the roduct$

Weight the soa instructor$

owder, determine the yield, and hand it to your

Report Sheet Cold Process

NameLLLLLLLLLLLLLLLLla* section LLLLLLLLLLLLL7ate

+y e of fat used LLLLLLLLLLLLLLLLLLLLLLLL

Weight of fat taken LLLLLLLLLLLLLLLLLLLLLg

Weight of Na:8 used LLLLLLLLLLLLLLLLLLLg

Weight of soa formed LLLLLLLLLLLLLLLLLLLg

<se the weight of fat taken and the reaction to find the theoretical yield !weight# of soa *arM

+heoretical yield

LLLLLLLLLLLLLg

J yield > !actual yield !weight of soa formed#/theoretical yield# N 100> LLLLLLLLLLLLLJ

Report Sheet Hot Process

NameLLLLLLLLLLLLLLLLla* section LLLLLLLLLLLLL7ate

+y e of fat used LLLLLLLLLLLLLLLLLLLLLLLL

Weight of fat taken LLLLLLLLLLLLLLLLLLLLLg

Weight of Na:8 used LLLLLLLLLLLLLLLLLLLg

Weight of soa formed LLLLLLLLLLLLLLLLLLLg

<se the weight of fat taken and the reaction to find the theoretical yield !weight# of soa *arM

+heoretical yield

LLLLLLLLLLLLLg

J yield > !actual yield !weight of soa formed#/theoretical yield# N 100> LLLLLLLLLLLLLJ

Questions

1# Why do long chain fatty acids melt higher than short chain acidsM

,# Why may you use the same weight of fat in your soa re aration regardless of the ty e of fat)saturated or unsaturated) em loyedM

9# Why are &egeta*les fats !oils# li2uid, while animal fats are solidM

-# Why are naturally occurring fatty acids e&en)chainedM

B# Why do wa"es, 4aseline and mineral oil all feel greasy like fats, e&en though they are not triglyceridesM

.# What is soda ashM 8ow does it formM Why is it useful in water softeningM

C# <sing the same weights of fat and alkali, would you get more or less soa *y using (:8 instead of Na:8M

/# Why can you unclog a kitchen)sink drain *y ouring lye down into itM