CHEM 2423 Recrystallization of Benzoic Acid Dr.

Pahlavan
EXPERME!" 4 # P$rification # Recrystallization of Benzoic acid

P$r%ose&
a) To purify samples of organic compounds that are solids at room temperature
b) To dissociate the impure sample in the minimum amount of an appropriate hot solvent
E'$i%(ent ) Materials&
hot plate 125-mL Erlenmeyer flask ice stirring rod spatula
Bchner funnel impure ben!oic acid "eighing paper digital scales
rubber tubing #hose) ben!oic acid boiling stones #chips) filter paper
25 mL graguated cylinder 5$ mL beaker %el-temp apparatus
Disc$ssion&
The products of chemical reactions can be impure& 'urification of your products must be performed to remove
by-products and impurities& Li(uids are customarily purified by distillation) "hile solids are purified by
recrystalli!ation #sometimes called simply *crystallization*)&
+ecrystalli!ation is a method of purifying a solid& There are t"o types of impurities, those more soluble in a
given solvent than the main component and those less soluble& #-f there are any impurities that have the same
solubility as the main component) then a different solvent needs to be chosen&)
.hen organic substances are synthesi!ed in the laboratory or isolated from plants) they "ill obviously contain
impurities& /everal techni(ues for purifying these compounds have been developed& The most basic of these
techni(ues for the purification of organic solids is recrystalli!ation) "hich relies on the different solubilities of
solutes in a solvent& 0ompounds) "hich are less soluble) "ill crystalli!e first& The crystalli!ation process itself
helps in the purification because as the crystals form) they select the correct molecules) "hich fit into the crystal
lattice and ignore the "rong molecules& This is of course not a perfect process) but it does increase the purity of
the final product&
The solubility of the compound in the solvent used for recrystalli!ation is important& -n the ideal case) the
solvent "ould completely dissolve the compound to be purified at high temperature) usually the boiling point of
the solvent) and the compound "ould be completely insoluble in that solvent at room temperature or at !ero
o
0&
-n addition the impurity either "ould be completely insoluble in the particular solvent at the high temperature)
or "ould be very soluble in the solvent at lo" temperature& -n the former case) the impurity could be filtered off
at high temperature) "hile in the latter case the impurity "ould completely stay in solution upon cooling& -n the
real "orld) this "ill never happen and recrystalli!ation is a techni(ue that has to be practiced and perfected&
+egardless of crystalli!ation method) the purity of the solid can be verified by taking the melting point&
1 good #suitable) recrystalli!ation solvent "ill dissolve a large amount of the impure compound at temperatures
near the boiling point of the solvent& /mall amount of compound being purified should remain in solution at lo"
1
CHEM 2423 Recrystallization of Benzoic Acid Dr. Pahlavan
temperatures) bet"een appro2imately 25 and 35
o
0& Lo" solubility at lo" temperatures minimi!es the amount
of purified compound that "ill lose during recrystalli!ation&
1 suitable recrystalli!ation solvent should also be partially volatile in order to be easily removed from the
purified crystals& The solvent should not react "ith the compound being purified and it should have the boiling
point belo" the melting point of the compound being purified because solid melts before dissolves #oiling out)&
-n selecting a good recrystalli!ation solvent one should also consider flammability) to2icity) and e2pense&
-n selecting a solvent consider that like likes like& 'olar compounds dissolve polar compounds and non-polar
compounds dissolve non-polar compounds& The most commonly used recrystalli!ation solvents are presented in
the follo"ing table&
solvent formula polarity boiling point #
$
0)
"ater 425 very polar 1$$
ethanol 04604254 polar 78
methanol 04654 polar 95
dichloromethane 0420l2 slightly polar :$
diethyl ether #046042)25 slightly polar 65
5rganic compounds "ith one polar functional group and a lo" number of carbon atoms such as methanol)
ethanol) and n-propanol are highly soluble #miscible) in "ater& These alcohols form hydrogen bond "ith "ater
due to the polar 354 functional group& 1s the number of carbons per polar functional group increase) solubility
decreases& The solubility of alcohols "ith four to five carbons is given in the follo"ing table&
0ompounds "ith si2 or
more carbons for each polar group "ill not be very soluble in polar solvents but "ill be soluble in non-polar
solvents such as ben!ene and cyclohe2ane&
-f a single solvent cannot be found that is suitable for recrystalli!ation) a solvent pair often used& The solvents
must be miscible in one another& /ome commonly used solvent pairs are "ater-ethanol) acetic acid 3 "ater)
ether-acetone& Typically) the compound being recrystalli!ed "ill be more soluble in one solvent than the other&
The compound is dissolved in a minimum amount of the hot solvent in "hich it is more soluble&
The follo"ing formulas used in solubility problems&
* lost in cold solvent ; #solubility in cold solvent<solubility in hot solvent) 21$$
* recovery of solid ; =g #solid ) 3 g #solid lost)> 2 1$$ < g #solid)
alcohol formula /olubility #g<1$$ ml 425)
n-butanol 04604204204254 8
n-pentanol 04604204204204254 2
n-he2anol 04604204204204204254 $&5
n-pentanol 04604204204204204204254 $&1
2
CHEM 2423 Recrystallization of Benzoic Acid Dr. Pahlavan
E+a(%le ,-.- The solubility of solid ?@A in hot "ater #5&5$ g<1$$ ml at 1$$
o
0) is not very great) and its
solubility in cold "ater #$&56 g<1$$ml at $
o
0) is significant& .hat "ould be the ma2imum theoretical percent
recovery from crystalli!ation of 5&$$ g of solid ?@A from 1$$ ml "aterB 1ssuming the solution is chilled at $
o
0&
'ercent solid lost in cold "ater ; #solubility in cold "ater< solubility in hot "ater) 21$$
; #$&56<5&5$) 21$$ ; /.04*
grams solid lost in cold "ater ; grams mass of original solid 2 percent lost ; 5&$$ g 2 C&9:D ; 1.422 3
g #solid recovered) ; g #solid) 3 g #solid lost) ; 5&$$ 3 $&:82 ; 4.42 3
D recovery ; g #solid recovered) 21$$ < g #solid) ; #:&52<5&$$) 21$$ ; /1.4 *
E+a(%le ,2. 3 The solubility of compound ?@A in ethanol is $&8$ g per 1$$ ml at $
o
0 and 5&$$ g per 1$$ ml at
78
o
0& .hat is the minimum amount of ethanol needed to recrystalli!e a 12&$$ g sample of compound ?@AB 4o"
much "ould be lost in the recrystalli!ation) that is) "ould remain in the cold solventB
amount of ethanol needed at 78
o
0 ; #12&$$ g)# 1$$ ml<5&$$ g) ; 241 (l
amount of sample remaining in the cold solvent at $
o
0 ; #2:$ ml)#$&8$ g<1$$ ml) ; -./ 3
or D lost ; #$&8$<5&$$) 21$$ ; 19 D 12&$$ 2 19D ; 1&C2 g
The actual laboratory "e "ill do is the recrystalli!ation of ben!oic acid from "ater using the temperature
gradient method& Ben!oic acid is not very soluble in cold "ater) but it is soluble in hot "ater& The purpose of
this e2periment is to learn the techni(ue of recrystalli!ation by purifying ben!oic acid&
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CHEM 2423 Recrystallization of Benzoic Acid Dr. Pahlavan

E+%eri(ental Proced$res

Esing a "eighing paper) "eigh out about 1&$$ g of ?impure Ben!oic acid for recrystalli!ationA and transfer it to
a 125-ml Erlenmeyer flask& 1dd about 2$ ml distilled "ater) using a graduated cylinder) to the flask and bring
the mi2ture to the boiling point by heating on a hot plate) "hile stirring the mi2ture and boiling gently to
dissolve ben!oic acid completely& #Fig 1)

ben!oic acid
solution
Erlenmeyer
flask
hot plate
Fig 1- Gissolving ben!oic acid
+emove the flask from the hot plate and e2amine the solution& -f there are particles of ben!oic acid still
undissolved) then add an additional amount of hot or cold "ater in small increments and resume heating the
solution& The obHective is to dissolve the entire solid in only as much as hot or near boiling solvent #"ater) as is
necessary& Go not add too much "ater or the solution "ill not be saturated and the yield of purified ben!oic
acid "ill be reduced& Ieep adding "ater in small amounts #several drops at a time from a 'asteur pipette) until
all of the ben!oic acid is dissolved and the solution is boiling&
-f the solution is completely clear #though not necessarily colorless) and no solid ben!oic acid is visible) then
add additional 1$-15 ml "ater to the mi2ture and place the Erlenmeyer flask on a countertop "here it "ill not
be disturbed and cover "ith an upside-do"n small beaker #to prevent dust contamination)& 1llo"ing the flask to
cool slo"ly "ill give the best-shaped crystals after about 5-1$ minutes& -f crystalli!ation does not occur after 1$
minutes) scrape the sides of the flask above the level of the solution "ith the sharp end of a glass rod hard
enough to audibly scratch the interior surface of the flask& This may dislodge some undetectable) small crystals
that "ill drop into the solution and *seed* the solution) helping to induce crystalli!ation& 1 seed crystal can
serve as a nucleation point for the crystalli!ation process& 0ooling the solution in an ice bath may also help at
this point&
:
CHEM 2423 Recrystallization of Benzoic Acid Dr. Pahlavan
.hen the crystals have formed completely #may re(uired ice bath)) collect your solid chemical by setting up a
vacuum #suction) filtration on a properly fitted filter paper in a clean Bchner funnel apparatus as described by
your instructor& #Fig 2)

vacuum#suction)
filtrate
ben!oic acid
Buchner
funnel

Fig& 2 3 Bchner funnel and suction flask
'our the chilled mi2ture into the Buchner funnel& The "ater should filter (uickly - if not) check for vacuum
leaks& Jet all the crystals out of the flask using a spatula or stirring rod& +insing "ith 1 or 2 mLs of cold "ater
helps get the crystals out of the flask) and rinsing helps remove impurities&
Let the aspirator run for a fe" minutes to start air-drying the crystals& Then use a spatula to lift the filter paper
and crystals out of the Buchner funnel) then press them as dry as possible on a large clean paper to"el #hand
dry)) allo" them to dry completely) and transfer the dry sample to a pre-"eigh "eighing paper& Getermine the
"eigh the G+K crystals of recovered ben!oic acid&
0alculate the percent recovered using the follo"ing written formula and determine the melting point of your
recrystalli!ed ben!oic acid&
5ei3ht of 6enzoic acid o6tained after recrystallization
* Recovered 7 +-11
5ei3ht of 6enzoic acid 6efore recrystallization
!ote& 8$6(it %rod$ct to the instr$ctor in a %ro%erly la6eled container.
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CHEM 2423 Recrystallization of Benzoic Acid Dr. Pahlavan
EXPERME!" 4 9 Recrystallization of Benzoic Acid
Data and Res$lts ,Recrystallization.
REP:R" ;:RM !a(e LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
nstr$ctor <<<<<<<<<<<<<<<<<<<<<<<<<<<

Date <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<
-. 8a(%le na(e <<<<<<<<<<<<<<<<<<<<<<<<<<<<
2. Data on the i(%$re Benzoic acid
a. Mass of the 6enzoic acid = >ei3hin3 %a%er <<<<<<<< 3

6. Mass of >ei3hin3 %a%er <<<<<<<< 3
c. Mass of i(%$re 6enzoic acid <<<<<<<< 3

3. Data for recrystallized 6enzoic acid

a. Mass of recrystallized 6enzoic acid = >ei3hin3 %a%er <<<<<<<<3
6. Mass of >ei3hin3 %a%er <<<<<<<< 3

c. Mass of recrystallized 6enzoic acid <<<<<<<<3
d. Calc$lation of %ercenta3e recovery
,sho> calc$lation.
<<<<<<<<*
d. Meltin3 %oint of recrystallized 6enzoic acid <<<<<<<<
o
C

e. 8tr$ct$ral for($la of the 6enzoic acid

9
CHEM 2423 Recrystallization of Benzoic Acid Dr. Pahlavan
Pre#?a6oratory @$estions9EXP 4 !a(e&
D$e 6efore la6 6e3ins. Ans>er in s%ace %rovided.

1& .hat is the ideal solvent for crystalli!ation of a particular compoundB .hat is the primary consideration in
choosing a solvent for crystalli!ing a compoundB
2& -mpure ben!oic acid "as dissolved in hot "ater& The container of solution "as placed in an ice-"ater bath
instead of being allo"ed cooling slo"ly& .hat "ill be the result of cooling the solution in this mannerB
6& 5utline the successive steps in the crystalli!ation of an organic solid from a solvent and state the purpose of
each operation&
:& 0ompound @ is (uite soluble in toluene) but only slightly soluble in petroleum ether& 4o" could these
solvents be used in combination in order to recrystalli!e @B
5& $&12 g of compound ?KA dissolves in 1$ ml of acetone at 25
o
0 and $&85 g of the same compound dissolves
in 1$ ml of boiling acetone& .hat volume of acetone "ould be re(uired to purify a 5&$ g sample of
compoundB

7
CHEM 2423 Recrystallization of Benzoic Acid Dr. Pahlavan
Post#?a6oratory @$estions9EXP 4 !a(e&
D$e after co(%letin3 the la6.
1& Jive some reasons "hy /uction filtration #vacuum) is to be preferred to gravity filtration&
2& 1 student recrystalli!ed some impure ben!oic acid and isolated it by filtration& 4e scraped the purified
ben!oic acid off the filter paper after it had dried and took the melting point as a test for purity& 4e "as
surprised that most of the "hite solid melted sharply bet"een 121 and 122
o
0 but that a small amount
remained unmelted even at temperatures above 2$$
o
0& E2plain this behavior&
6& .hat does the term ?oiling outA meanB 4o" can one prevent oiling outB
6& .hat are the purposes of the follo"ing in recrystalli!ation of solidsB
-) boiling stones 3
--) activated carbon -
---) seed crystals 3
:& Jive one reason "hy "e cannot reuse boiling chipsB
5& $&12 g of compound ?KA dissolves in 1$ ml of acetone at 25
o
0 and $&85 g of the same compound
dissolves in 1$ ml of boiling acetone& -f 5&$ g of compound ?KA "ere to be recrystalli!ed from 75 ml
acetone) "hat "ill be the ne2t ma2imum amount of ?KA that "ill be recrystalli!edB
8