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+ HB
K
eq
K
eq
=
[A
-
] [HB]
[HA] [B
-
]
K
eq
=
K
a(HA)
K
a(HB)
Freshman Research Initiative: Synthesis and Biological Recognition stream
Section 1: Solubility, Acids & Bases and Solutions
Experiment 3: Two-Base Extraction
6
The ueiivation foi equation 4 can be founu on the SBRS website:
sbis.cm.utexas.euuexpS. Taking the negative log of the expiession in equation 4
gives:
345./#1, J
Keep in minu that "p" stanus foi the negative log of Keq. To analyze the
uiiection that the equilibiium lies, we must look at Keq, oi even log1uKeq will give us
the coiiect sign (+ oi -) foi the expiession.
Equation S is key foi unueistanuing this expeiiment. We can use equation S
to analyze if a paiticulai base is stiong enough to uepiotonate the aciu that we wish
to conveit to its conjugate base. If log1uKeq is > 1, the foiwaiu ieaction in equation 2
is favoieu, anu the equilibiium will lie to the iight, favoiing the foimation of A
-
anu
BB. If log1uKeq < 1 then the equilibiium is favoieu to the left, meaning that most of
the staiting aciu is unuissociateu; BA anu B
-
exist piimaiily in solution.
Let us put this concept into piactice by consiueiing the sepaiation we wish to
peifoim in this expeiiment. Both ;-toluic aciu anu ;-0$+0-butylphenol aie piotic
acius; tieatment with a stiong enough base will uepiotonate these acius anu conveit
them to watei-soluble anions. If we can uepiotonate one of these acius F&0="D0
uepiotonating the othei, we will be able to paitition the unuissociateu aciu into the
oiganic layei anu the conjugate base we foim selectively into the aqueous layei.
The most aciuic compounu is the caiboxylic aciu; let's consiuei the uepiotonation of
;-toluic aciu with Na0B (Scheme 1).
:%?("( 6
We can now solve foi pKeq: 4.2-1S.7 = -11.S. Beai in minu that this is pKeq
to conveit it to log1uKeq we just neeu to change the sign. Log1uKeq is theiefoie 11.S,
which means that Na0B is an excellent base foi the uepiotonation of ;Gtoluic aciu.
The equilibiium foi this ieaction lies fai to the iight. ;-Toluic aciu woulu be
effectively conveiteu to its conjugate base (I), which will be soluble in the aqueous
layei.
0ui methou to sepaiate the aciuic components of the mixtuie will only be
successful if ;-0$+0-butylphenol is not also uepiotonateu by Na0B. This will allow
this component to iemain in the oiganic layei, while the ;-toluic aciu conjugate base
goes into the watei layei. Let's examine the ieaction of ;-0$+0-butylphenol with
pK
eq
= pK
a(HA)
- pK
a(HB)
O
OH
1
pK
a
= 4.2
3
pK
a
= 15.7
O
O
+ +
2 4
Na OH
H
2
O
Na
Freshman Research Initiative: Synthesis and Biological Recognition stream
Section 1: Solubility, Acids & Bases and Solutions
Experiment 3: Two-Base Extraction
7
hyuioxiue (Scheme 2). Because the souium ion appeais on both the ieactant anu
piouuct siue, it has been omitteu in this scheme.
:%?("( G
If we again peifoim oui pKeq analysis, we get: 1u-1S.7 = -S.7. Log1uKeq is S.7
anu again the equilibiium is favoieu to the iight! This means that if we tieat a
mixtuie of ;-0$+0-butylphenol anu ;-toluic aciu with Na0B, we will foim the
conjugate bases of both acius, ienueiing them /"0= watei-soluble. They will both go
into the aqueous layei, anu we will be unable to sepaiate these components.
We neeu to use a weakei base to selectively uepiotonate the caiboxylic aciu
in the piesence of the phenol. Among the bases available to us aie caibonate
(commeicially available as souium caibonate) anu bicaibonate (in the foim of
souium bicaibonate). Scheme S shows the ieaction of each of these bases with aciu.
:%?("( H
The spontaneous conveision of caibonic aciu to gaseous C02 piesents a
piactical pioblem when caibonate anu bicaibonate aie useu to uepiotonate acius,
especially when peifoiming extiactions using a sepaiatoiy funnel. Namely, the
piessuie that iesults fiom the foimation of caibon uioxiue can iesult in a builu up of
piessuie in a closeu vessel. If the sepaiatoiy funnel is useu impiopeily, it can builu
up piessuie anu spew the contents of the sepaiatoiy funnel all ovei you anu youi
labmates. If the solvent is volatile enough, it can cause the funnel to exploue, anu
this has iesulteu in one veiy seiious injuiy that I know of.
K?5$L +15 "5$/ (C(*%#$( %.*( A?(, ,(5/*.'#<#,- .%#)$ A#/? %.*&1,./( 1*
&#%.*&1,./(= 0se of hyuioxiue ion as a base uoes not suffei fiom this pioblem, so it
is often piefeiable to use hyuioxiue ion to neutialize acius. Bowevei, in the
extiaction expeiiment you will peifoim, it is essential to use bases in a specific
oiuei, as you will leain.
0sing souium bicaibonate is not oveily uangeious if the sepaiatoiy funnel is
useu coiiectly. Souium bicaibonate shoulu be auueu into the sepaiatoiy funnel, anu
OH
5
pK
a
= 10
3
pK
a
= 15.7
O
+ + OH
H
2
O
7 6
O O
O
+ H
3
O
+
HO O
O
+ H
3
O
+
HO OH
O
CO
2
+ H
2
O
pK
a
= 10.3 pK
a
= 6.4
carbonate bicarbonate carbonic acid
Freshman Research Initiative: Synthesis and Biological Recognition stream
Section 1: Solubility, Acids & Bases and Solutions
Experiment 3: Two-Base Extraction
8
then you shoulu wait foi the stiong effeivescence to slow uown. uently swiil the
funnel without its stoppei to slowly mix the layeis until the evolution of gas is not
too stiong. 0nce the evolution of caibon uioxiue has subsiueu, the funnel may be
stoppeieu, inveiteu, anu the stopcock openeu to vent the mixtuie. H$#$#/$+ 0='0
0=$ )0";<"<I )="D.@ "5.> /$ ";$5$@ F=$5 0=$ *D55$. &) =$.@ &5 '5 &5E$+0$@ ;")&0&"5
(Figuie 4). Repeat this opeiation two oi thiee times. The stopcock can now be
closeu again, the mixtuie shaken gently, anu venteu. Fiequent venting is the key to
using souium bicaibonate safely:
Let us now consiuei what woulu happen if we tieat ;-toluic aciu (6) anu ;-
0$+0-butylphenol (J) with souium bicaibonate (G) (Schemes 2 anu S). In the
ieaction of ;-toluic aciu with bicaibonate (Scheme 2), the equilibiium lies to the
iight, favoiing the foimation of the ;-toluate anion. This is because ;-toluic aciu (6)
is a stiongei aciu than caibonic aciu H (&6$61 the pKa of ;-toluic aciu is lowei), so it
gives up a pioton to bicaibonate moie ieauily than the ieveise ieaction will occui.
:%?("( I
The situation changes when we attempt to use souium bicaibonate G to
uepiotonate ;-0$+0-butylphenol J (Scheme S). Now caibonic aciu is the stiongei
aciu, anu is theiefoie moie likely to give up a pioton to M. This means that the
equilibiium will lie to the left. Note that the equilibiium aiiow ieflects this.
O
OH HO O
O
1
pK
a
= 4.2
HO OH
O
9
pK
a
= 6.4
O
O
+ +
8 4
Na
Na
Freshman Research Initiative: Synthesis and Biological Recognition stream
Section 1: Solubility, Acids & Bases and Solutions
Experiment 3: Two-Base Extraction
9
:%?("( J
We have toucheu on an impoitant point that gives insight as to how we will
sepaiate oui piotic acius in this lab. ;-Toluic aciu (6) can be uepiotonateu with
souium bicaibonate (N), which will ienuei its conjugate base I soluble in the
aqueous phase, oi watei layei. We can sepaiate the aqueous bicaibonate layei, anu
then aciuify it to iefoim ;-toluic aciu (6), which is insoluble in watei (Scheme 6).
We will then be able to use a new technique foi the isolation of piecipitates calleu
vacuum filtiation to sepaiate the soliu fiom the watei.
:%?("( O
We still neeu a methou to sepaiate the ;-0$+0-butylphenol 6P fiom 1,4-
uimethoxybenzene. We have alieauy shown that ;-0$+0-butylphenol can be
uepiotonateu using hyuioxiue (Scheme 2). Because the ;-toluic aciu has alieauy
been sepaiateu fiom the mixtuie, we neeu not woiiy about both bases being
uepiotonateu simultaneously. We may then sepaiate the aqueous Na0B layei fiom
the oiganic layei using the sepaiatoiy funnel anu selectively iemove the conjugate
base of ;-0$+0-butylphenol.
Now how will we sepaiate the 1,4-uimethoxybenzene. The answei is
simple: 1,4-uimethoxybenzene is the only component iemaining in the oiganic
phase. We can simply collect the oiganic layei, iemove any iesiuual watei fiom the
oiganic layei using a uiying agent, iemove the uiying agent by (+'E&0> filtiation, anu
iemove the solvent by iotaiy evapoiation. You've uone this piocess alieauy in
Expeiiment 1.
Q1 /1 R00(,)#C S 21* . 2'1A %?.*/ 15/'#,#,- 12 15* 1@(*.'' 05*#2#%./#1,
$/*./(-+= T'(.$( *(@#(A /?( 2'1A %?.*/ /?1*15-?'+ &(21*( %1"#,- /1 '.&=
In the lab, you may use a beakei oi an Eilenmeyei flask to combine youi
washes. An Eilenmeyei is geneially piefeiieu in a typical extiaction, as the shape
ieuuces iapiu evapoiation of solvents like ethei, allowing foi uiying of the volatile
OH
HO O
O
5
pK
a
= 10
HO OH
O
9
pK
a
= 6.4
O
+ +
8 7
O
O
H
3
O
+
O
OH
4
water-
soluble
1
water-
insoluble
Freshman Research Initiative: Synthesis and Biological Recognition stream
Section 1: Solubility, Acids & Bases and Solutions
Experiment 3: Two-Base Extraction
10
oiganic layei with a uiying agent. Auuitionally, the shape of an Eilenmeyei allows
foi the stem of the sepaiatoiy funnel to be placeu uiiectly below the lip, which
pievents splashing while the liquiu is uiopping in fiom the sepaiatoiy funnel.
Be ceitain to put all thiee NaBC0S layeis into one containei, but B0 N0T
C0NBINE these poitions with those fiom the Na0B extiactions. The final layei is
also saveu sepaiately, anu this is the oiganic layei that contains the 1,4-
uimethoxybenzene.
3UT3VDW38K IL TRVK G9 WDXVY:XRZ3 :3TRVRKDY8:
When peifoiming stiuctuieu expeiiments in the lab, it is simple foi us to
giab a couple giams of a compounu anu go. When caiiying out a synthesis, you may
not have this much mateiial on youi hanus. If you stait with a giam of youi staiting
compounu anu have two steps wheie you get Su% yielu on each. well, you can see
wheie this is going.
In piactice, we sometimes woik on scales unuei 1uu mg, anu we have to
scale eveiything uowneven the woikup. Imagine tiying to shake 2 mL of liquiu in
a 6u-mL sepaiatoiy funnel, which is the smallest funnel we have in lab. You woulu
lose most of the liquiu onto the siues, anu even with caieful, quantitative
tiansfeiiing you woulu lose some piouuct.
Foi this ieason, we sometimes peifoim extiactions in vials. The concept is
the same: we neeu to iemove one layei selectively; howevei, we uon't have the
luxuiy of a stopcock when using a vial. We have to sepaiate oui immiscible liquius
using a Pasteui pipet, anu theie aie a few tiicks to uoing this.
Fiist anu foiemost, clamp eveiything. vials tenu to topple easily, so you will
want to make suie both youi extiaction vial anu the vial you'ie tiansfeiiing into aie
secuieu. A nice tiick foi keeping youi vials upiight without clamping them is to use
an inveiteu coik iing. Simply flip ovei the smallest coik iing we have, anu stanu the
vial up in the hole.
Keep youi glasswaie close. If you'ie tiansfeiiing uiethyl ethei, which is veiy
volatile, it is uifficult to pievent it fiom uiipping. By having youi vials siue by siue
(oi even holuing one in youi hanu to keep the mouths veiy close) you can pievent
most spillage when tiansfeiiing.
To iemove the bottom layei, you can simply put the pipet all the way to the
bottom anu suck up the layei. Removing the top layei is pietty stiaightfoiwaiu as
well. Simply suck up the entiie layei anu pipet it into youi new vial. It can be
uifficult to iemove the entiie layei, but theie is a tiick to this as well. Suck up the
entiie top layei, anu some of the bottom layei. Allow the layeis to sepaiate in the
Pasteui pipet, anu then caiefully uiip the bottom layei back into the vial. Befoie you
begin the seconu pait of this expeiiment, be suie to piactice this technique a bit by
putting 2 mL of uiethyl ethei anu 2 mL of watei in a 4-uiam vial anu tiying to
iemove each layei selectively.