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Chemical Separations

What is a chemical separation?


Examples:
Filtration
Precipitations
Crystallizations
Distillation
HPLC
GC
Solvent Extraction
Zone Melting
Electrophoresis
Mass Spectroscopy
Chemical Separations

What is the object of the separation.


Collection of a pure product
Isolation for subsequent analysis for either quantification or
identification
Analysis
How Much?
What is it?
Chemical Separations

Major Industries

Petroleum Distillation

Distilled Spirits
Chemical Separations

Petroleum is a mixture of hydrocarbons.

The larger the molecular weight the less volatile.

So we must separate into various molecular weight


fractions (different boiling points)

The results are still complex mixtures


Chemical Separations

Solvent Extraction

http://oceanexplorer.noaa.gov/explorations/02sab/background/products/products.html
Solvent Extraction
Replace concentration with moles over volume
and let q equal the fraction in the aqueous phase
Define a new term for the ratio of the
volumes of the phases
We can do a little algebra and find an
expression for q
Since if it does not end up in the aqueous phase it
must be in the organic.

p is the term for the fraction in the organic


p+q = 1

Giving
Sample Problem

You have 100.0 mL of an aqueous solution that


is 100.0 mM in compound C. This solution is
extracted with 50.0 mL of diethyl ether and the
aqueous phase is assayed and it is found that
the concentration of compound C that remains is
20.0 mM. What is the equilibrium constant for
this extraction system.
Solution
We can do multiple extraction from the
aqueous phase.
We end up with the following expression for what is
left in the aqueous phase.
Example

How many extractions would be required to remove


99.99% of aspirin from an aqueous solution with an
equal volume of n-octanol?

Since 99.99% must be removed the decimal fraction


equivalent of this is 0.9999. This leaves 0.0001 in the
aqueous phase. Since we have equal volumes then Vr
is 1.00.

We are able to find from the Interactive Analysis Web


site that K for Aspirin is 35.5. We plug these values into
the q equation and the power is the unknown.
Solution
What if our compound can dissociate or
participate in some other equilibrium?

A compound such as aspirin is a carboxylic


acid. We can represent this as HA.

Do we expect the ion A- to be very soluble in


the organic phase???
Dissociation

So if we have dissociation then less will go


into the organic phase.

Kp is the ratio of concentration of aspirin (in


the un-dissociated form) in each phase. This
ratio will always be the same.

How do we account for the ion formation?


Distribution Coefficient

Where C is the formal


concentration of the
species.
Ca = [HA] + [A-]
Dc will vary with
conditions
For this compound what
is that condition?
Dc

Since the ion is not very


soluble in the organic
phase then we may
assume that the
dissociation will not
happen in that phase.

This gives us the


expression to the right.
Acid Equilibria

What is the equilibrium?


Ka
With a little algebra

So if you know Kd and Ka


then you can determine Dc
as a function of H+ (pH)

However if [H+] is much


larger than Ka then Dc will
equal Kd. If the [H+] is close
in value to Ka then D will be
related to the pH

Plotting this we get.


So What, Why is this useful.
Well we can now move a solute (analyte) from one phase to another.
This can be very useful when extracting a compound that has
significant chemical differences from other compounds in solution. As a
matter of fact this has been used as an interview question for
prospective co-ops when I worked in industry.
The question would go like this. You have carried out a series of
reactions and it is now time to work up the product which currently sits
in an organic solution (methylene chloride). Your expected product is a
primary amine. Which of the following solutions would you extract this
methylene chloride solution with to isolate your amine.

Your choices are:


A) Toluene.
B) 0.1 N NaOH (aq)
C) 0.1 N HCl (aq)
D) I never wanted to work here anyhow.
Separation

So far we can tell how one compound moves


from one phase to another. What if we are try
to separate two compounds, A and B

Well we might just suspect that if we find a


solvent system that has different values of Dc
for each compound we could end up with most
of one compound in one phase and the other
compound in the opposite phase. It is not that
simple.
Example

System I
Da = 32 Db = 0.032 (A ratio of 1000)
Vr= 1
Let's recall our equations
q (fraction in aqueous) = 1 / (DVr + 1)
p (fraction in organic) = DVr / (DVr + 1)
Vr (volume ratio) = Vo / Va
Case I

pa = 32*1 / (32*1 + 1) = 0.97


pb = 0.032*1/ (0.032*1 + 1) = 0.03
If we assume that we have equal moles of A
and B to start then what is the purity of A in
the Organic Phase?
Purity = moles A / (moles A + moles B)
Purity = 0.97 / (0.97 + 0.03) = 0.97 or 97 %
Case II

Da = 1000 Db = 1 VR = 1 (Ratio is still 1000)


pa = 1000*1 / (1000*1 + 1*1) = 1000/1001 = 0.999
Aha! we got more a into the organic, as we would expect with a
higher D value.
Now
pb = 1*1 / ( 1*1 +1) = 1/2 = 0.5
oh-oh
What do we get for purity of compound a now?
purity = 0.999 / (0.999 + 0.50) = 0.666
Yuck!
How can we get around this issue?

Once we have selected the solvent and pH, then there is little
that we can do to change D. What else do we have in our
control?????

Let's look
p = DVr / (DVr + 1)
Not much here except Vr and in fact that is the key to this
problem. Is there an optimum Vr value for the values of D that
we have? Yes!
Our equation for this is V r(opt) = (Da*Db)-0.5
Revisit the two cases

So let us look at our two cases and see which


will give us the optimum values.
Case I
Da = 32 and Db = 0.032

V r(opt) = (32 * 0.032)-0.5 = ( 1 )-0.5 = 1


So we were already at the optimum.
Case II Revisited

Case II
Da = 1000 and Db = 1
Vr (opt) = (1000*1)-0.5 = 1000-0.5 = 0.032
Which mean that when we do our extraction
we will extract _______ mL of organic for
each _______ mL of aqueous.
Purity for Case II

What is our purity for this system?


pa = 1000*0.032 / (1000*0.032 + 1) = 32/33 = 0.97
and
pb = 1*0.032 / (1*0.032 + 1) = 0.032/1.032 = 0.03

Purity of a then is 0.97/ (0.97 + 0.03)

Which will give us the 97% purity we had for Case I with with the Vr of 1.
Can we improve this purity?
If we were to extract again then we would just
remove the same proportions. We would get
more compound extracted but it would be the
same purity.

What if we were to take the organic phase


and extract it with fresh aqueous phase. We
know that one of the two compounds will end
up mostly in that aqueous phase so we
should enhance the purity of the other
compound in the organic phase.
Back Extraction

Called that since you are extracting back into


the original phase.
Back Extraction
Case I Example

Let's look at the numbers.


Da = 32
Db = 0.032
Vr = 1

pa = 0.97
pb = 0.03

qa = 0.03
qb = 0.97

Lets prepare a table.


Initial conditions
prior to starting back extraction

.
Before Shaking Amount A Amount B
Organic Phase 0.97 0.03
Fresh Aqueous Phase 0 0
Now we extract shake shake shake

How much goes to the Aqueous phase


q which is 0.03 for A and 0.97 for B

How much goes to the Organic phase


p which is 0.97 for A and 0.03 for B

After Shaking Amount A Amount B


Organic Phase (0.97)(0.97) (0.03)(0.03)
Aqueous Phase (0.97)(0.03) (0.03)(0.97)
Now what is the purity for A in the organic phase???

Purity = Amount A / (Amount A + Amount B) =

0.97*0.97 / (0.97*0.97 + 0.03*0.03) =

0.94/(0.94 + 0.0009) = 99.9%

What is the yield of A (fraction of the total amount that we


started with)
Lets do it again Can we improve purity
even more?

After second Back Extraction Amount A Amount B


Organic Phase 0.94*0.97 0.0009*0.03
Aqueous Phase 0.94*0.03 0.0009*0.97

Purity A = 0.913 / (0.913 + 0.000027) = 99.997%


But our yield has dropped to 91.3%, there is a price to pay for the added purity.
Can We Expand This?
Why Would We Want to?
Such multiple extraction systems have been
developed.
Still a viable option for preparative work.
For separations it has been replaced by HPLC

Called Craig Counter Current Extraction.


Special glassware is used.
Craig CCE

Equal amounts of organic (red) and


aqueous (blue) solvents with the
analyte(s) are added to the A arm of
the tube via port O. Fresh Aqueous
Solvent is added to each of the tubes
down the apparatus.
Craig CCE

Rock the system


back and forth and
to establish
equilibrium.
Allow the system to
stand for the layers
to separate.

Rotate the
apparatus counter
clockwise about 90o
to 100o.
Craig CCE

Rotate Back to Horizontal


Starting Conditions

Tube# 0 1 2 3 4
Organic
0
Phase
Aqueous
1 0 0 0 0
Phase

After One Equilibrium

Tube# 0 1 2 3 4
Organic Phase p
Aqueous Phase q 0 0 0 0

Transfer Step 1

Tube# 0 1 2 3 4
Organic Phase 0 p
Aqueous Phase q 0 0 0 0
Now here is what is in each tube/phase after equilibrium is reached.

Tube# 0 1 2 3 4
Organic
pq pp
Phase
Aqueous
qq qp 0 0 0
Phase

Now we do Transfer 2

Tube# 0 1 2 3 4
Organic Phase 0 pq pp
Aqueous Phase q2 pq 0 0 0
Now here is what we have in each tube after the next equilibrium.
The total in each tube times either p or q as appropriate.

Tube# 0 1 2 3 4
Organic
pq2 p*2pq p3
Phase
Aqueous
q3 q*2pq qp2 0 0
Phase

We transfer again.

Transfer Step 3

Tube# 0 1 2 3 4
Organic Phase 0 pq2 2p2q p3
Aqueous Phase q3 2pq2 p2q 0 0
Shake Again Equilibrium 4

Tube# 0 1 2 3 4
Organic
pq3 p*3pq2 p*3p2q p4
Phase
Aqueous
q4 q*3pq2 q*3p2q q*p3 0
Phase

Transfer 4

Tube# 0 1 2 3 4

Organic Phase 0 pq3 3p2q2 3p3q p4

Aqueous Phase q4 q*3pq2 3p2q2 p3q 0

See a trend????
Craig CCE

How about a binomial expansion?


(q + p)n = 1

Powers of the two terms in each tube will add up to n


Coefficients will be found from Pascal Triangle
1
1 1
1 2 1
1 3 3 1
1 4 6 4 1
1 5 10 10 5 1
1 6 15 20 15 6 1
1 7 21 35 35 21 7 1
Craig CCE

Or the formula

Fr,n = n!/((n-r)!r!) pr q(n-r)

n is the number of transfer and r is the tube


number. You start counting at zero!
Craig CCE

Let's look at and example for a four tube system.


Da = 3 p = 0.75 q = 0.25
Db = 0.333 p = 0.25 q = 0.75

What would be the purity and yield of Compound A if collected from


the last in our above example.

Amount of A p4 or 0.754 = 0.3164


Amount of B p4 or 0.254 = 0.0039
Purity of A 0.3164 / (0.3164 + 0.0039) = 0.9878 or 98.78%

Yield of A We collect a fraction of 0.3164 or 31.64%

Horrible Yield!
Craig CCE

What if we collect the last two tubes??


Amount of A p4 and 4p3q or 0.754 +
4*(0.75)3(0.25) = 0.3164 + 0.4219 = 0.7383
Amount of B p4 and 4p3q or 0.254 +
4*(0.25)3(0.75) = 0.0039 + 0.0469 = 0.0508
Purity of A (0.3164 + 0.4219) / (0.3164 + 0.4219 +
0.0039 + 0.0469 ) = 0.9356 or 93.56%

Yield of A We collect a fraction of 0.3164 +


0.4219 = 0.7383 or 73.83 %
Purity still ok and yield is much better.
Craig system n= 200 transfers.
Da of 2.0 and Db of 4.0
pa of 0.666 pb of 0.800.
Animation Link

http://www.chem.uoa.gr/applets/AppletCraig/Appl_Craig2.html
Final Formulas(1)

rmax = np = nDVr/(DVr +1)


To find the separation between two peaks we
would use.
rmax = (rmax)a - (rmax)b = n(pa-pb)

The Gaussian distribution approximation for our


binomial expansion would be (when n>24)
Fr,n = (2)-0.5(npq)-0.5 exp-[((np-r)^2)/2npq]
Final Formulas(2)

The width of the distribution through the system


would be:
w = 4 = 4(npq)0.5
Resolution would be
R = rmax/w = rmax/4
or
R = np/(4(npq)0.5) = n0.5 p / 4(pq)0.5