CHEM 233 Lecture 4

Acid/Base Extraction
Spring 2014
 Liquid/liquid extraction
Extraction is a method to purify solids and liquids

• Extraction separates compounds based on relative

solubilities in liquids (partitioning)

• Use 2 immiscible solvents

• Typically use an aqueous and an organic solvent

 Immiscible liquids

Miscible liquids will mix together in all ratios

Immiscible liquids will separate in some ratios

Water & oil Water & Ethanol

Immiscible Miscible
liquids liquids
Layering
How do we determine which
liquid will be on the top or
bottom?

DENSITY

Liquids with higher density will “sink”

Liquids with lower density will “float”

Ex: oil and water

 Principle of Acid-Base Extraction
• Water dissolves ionic compounds
H
H H O O H
O H
H H H
O + O O
H H
H H H
O
H H O
H
• Organic solvents dissolve neutral organic
compounds
K
Xaq Xorg
[Xorg]
K= partitioning coefficient
[Xaq]

K > 1 for most organic cmpds

K < 1 for most salts

See later slides for quantitative analysis

of extractions using these principles
 Extraction Process Summary
1. Add solid mixture to organic solvent until fully
dissolved
– Choose solvent that dissolves all components of mixture
2. Pour organic solvent into separatory funnel, then
add aqueous solvent, close funnel with stopper, and
mix by inverting, then swirling gently
– Aqueous solvent can be either pure water or contain acidic, basic, or
neutral salts
3. Invert again and allow layers to separate, then drain
each layer into a separate container.
– Separatory funnel designed for this use (see notes on safe use from
Lecture 1 from Week 2)
4. Repeat as many times as necessary per layer to
efficiently extract dissolved materials.
5. Isolate desired compounds from each layer
– Organic: evaporate solvent Separatory
– Aqueous: precipitate compound and filter Funnel
 Step-By-Step Process

Let’s separate a mixture of these three solids using extraction:

1. Dissolve the mixture into dichloromethane

– All are neutral organics, mildly to moderately polar, and so moderate
polarity solvent will dissolve all three.
2. Add an aqueous solution and mix thoroughly

Which aqueous solution?

 Where will compounds go?

• Neutral organic compounds will partition into the organic

solvent layer
– Partition into = preferably dissolve in
• How do we then force organic compounds into the aqueous
layer?

MAKE THEM IONIC

Exploit functional groups by using acid/base chemistry
Extraction reagents
Extraction reagents
NEUTRAL ORGANIC
MOLECULES
CHARGED ORGANIC
MOLECULES
Dissolve in Organic Dissolve in Aqueous
Solvent Solvent
 Solubility/Ionization vs. pH
Neutral
Organic
Solubility

Aqueous Salt - Charged

pH
 Adding acid

Organic layer Organic layer Organic layer

If we add an acidic aqueous solution, what will happen?

Organic layer Aqueous layer Organic layer

Basic groups will become protonated and become ionic

Those molecules will partition into the aqueous layer

Separate the aqueous layer and save for later

 Adding base

Organic layer Organic layer

If we add a basic aqueous solution, what will happen?

Organic layer Aqueous layer

Acidic groups will become deprotonated and become ionic

Those molecules will partition into the aqueous layer

Separate the aqueous layer and save for later

 What about the organic layer?

This is the only compound left in the organic layer

Evaporate the solvent to leave only the solid compound
But first, it needs to be dried

Many organic solvents can mix with a small amounts of water

• Use a drying agent
• MgSO4
• Na2SO4s
• Add drying agent until flocculent
• Remove drying agent with gravity filtration
How about those aqueous layers?
We need to undo the process of making an ion

NEUTRALIZE

What is in the HCl extraction layer?

How would we neutralize the HCl extraction layer?

And the NaOH extraction layer?

 Finishing up
• Collect the precipitated product with vacuum filtration
• Dry products
• Take melting points

Successfully separated three compounds based on

their affinity for organic and aqueous solutions

Collected from Collected from Collected from

organic layer acidic layer basic layer
evaporation precipitation precipitation
 Notes on extractions
1. Make sure the stopcock is closed when
filling the separatory funnel
2. Hold stopper when shaking the separatory
funnel
3. Vent separatory frequently, always vent
away from yourself and others
4. Remove stopper before draining the
separatory funnel
5. Do not discard anything until 3 products are
obtained in solid form
6. Check for neutralization with pH paper
7. Shaking sodium hydroxide and methylene
chloride can form an emulsion
• Swirl or gently rock these extractions
 Partition Coefficient
At equilibrium, a portion of the compound will be in each solvent.
The ratio of concentrations in each layer is defined by the partition coefficient K

[𝐴]𝑜𝑟𝑔 𝐴 𝑖𝑛 𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑙𝑎𝑦𝑒𝑟

𝐾= ≡
[𝐴]𝑎𝑞 𝐴 𝑖𝑛 𝑎𝑞𝑢𝑒𝑜𝑢𝑠 𝑙𝑎𝑦𝑒𝑟

𝑛 𝑎𝑚𝑜𝑢𝑛𝑡 𝑚𝑎𝑠𝑠 𝑖𝑛 𝑔 𝑎𝑓𝑡𝑒𝑟 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑖𝑜𝑛

𝐴 = ≡
𝑉 𝑣𝑜𝑙𝑢𝑚𝑒 (𝑖𝑛 𝑚𝐿)

𝑛𝑜𝑟𝑔
𝑉𝑜𝑟𝑔 𝑛𝑜𝑟𝑔 𝑉𝑎𝑞
𝐾= 𝑛 =
𝑎𝑞 𝑛𝑎𝑞 𝑉𝑜𝑟𝑔
𝑉𝑎𝑞
 Single extraction example
If the partition coefficient between ether and water for compound A is 8.5,
what mass of A would be extracted from a solution of 10 g of compound A in
100 mL of water by a single extraction using 100 mL of ether?

First we need an equation in terms of the mass of the organic

𝑛𝑜𝑟𝑔 𝑉𝑎𝑞
𝐾= and 𝑛𝑡𝑜𝑡𝑎𝑙 = 𝑛𝑎𝑞 + 𝑛𝑜𝑟𝑔
𝑛𝑎𝑞 𝑉𝑜𝑟𝑔
𝑛𝑎𝑞 = 𝑛𝑡𝑜𝑡𝑎𝑙 − 𝑛𝑜𝑟𝑔

Substitute Solve for norg

𝑛𝑜𝑟𝑔 𝑉𝑎𝑞 𝐾 × 𝑛𝑡𝑜𝑡𝑎𝑙

𝐾= 𝑛𝑜𝑟𝑔 =
𝑛𝑡𝑜𝑡𝑎𝑙 − 𝑛𝑜𝑟𝑔 𝑉𝑜𝑟𝑔 𝑉𝑎𝑞
𝐾+
𝑉𝑜𝑟𝑔

See Next Slide…

 Single extraction example cont.
If the partition coefficient between ether and water for compound A is 8.5,
what mass of A would be extracted from a solution of 10 g of compound A in
100 mL of water by a single extraction using 100 mL of ether?

From previous slide

𝐾 × 𝑛𝑡𝑜𝑡𝑎𝑙 𝐾 = 8.5 𝑉𝑎𝑞 = 100𝑚𝐿
𝑛𝑜𝑟𝑔 =
𝑉𝑎𝑞
𝐾+ 𝑛𝑡𝑜𝑡 = 10𝑔 𝑉𝑜𝑟𝑔 = 100𝑚𝐿
𝑉𝑜𝑟𝑔
Plug in values

8.5 × 10𝑔
𝑛𝑜𝑟𝑔 = = 8.95𝑔
100𝑚𝐿
8.5 +
100𝑚𝐿
 Multiple extractions
From previous slide
If the partition coefficient between ether and water
for compound A is 8.5, what mass of A would be 𝐾 + 𝑛𝑡𝑜𝑡𝑎𝑙
𝑛𝑜𝑟𝑔 =
extracted from a solution of 10 g of compound A in 𝑉𝑎𝑞
𝐾+
100 mL of water by 4 extractions of 25 mL of ether? 𝑉𝑜𝑟𝑔

8.5 × 𝟏𝟎𝒈 𝒏𝒕𝒐𝒕𝒂𝒍 (g) 𝒏𝒐𝒓𝒈 (g) 𝒏𝒂𝒒 (g)

𝑛𝑜𝑟𝑔 = = 𝟔. 𝟖𝒈 Extraction
100𝑚𝐿
8.5 + 1st 10 6.8 3.2
25𝑚𝐿 n for 1st extraction
org 2nd 3.2 2.18 1.02
𝟏𝟎𝒈 − 𝟔. 𝟖𝒈 = 𝟑. 𝟐𝒈 3rd 1.02 0.69 0.33
naq becomes new ntotal 4th 0.33 0.22 0.11
8.5 × 𝟑. 𝟐𝒈
𝑛𝑜𝑟𝑔 = = 𝟐. 𝟏𝟖𝒈 Sum of norg is total mass extracted
100𝑚𝐿
8.5 +
25𝑚𝐿
𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑒𝑑
Iterate as appropriate to fill in table = 6.8 + 2.18 + 0.69 + 0.22
= 9.89𝑔
 Multiple extractions cont.
We now see that, given the same total extraction solvent volume, combining
iterated small-volume extractions will be a more efficient use of that volume
than a single, large-volume extraction

𝑛𝑜𝑟𝑔 𝑉𝑎𝑞 𝑉𝑎𝑞

𝑟
𝐾= 𝑛𝑎𝑞 = 𝑛𝑡𝑜𝑡𝑎𝑙
𝑛𝑎𝑞 𝑉𝑜𝑟𝑔 𝑉𝑎𝑞 +𝐾𝑉𝑜𝑟𝑔
𝑟 ≡ 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑖𝑜𝑛𝑠 𝑜𝑓 𝑒𝑞𝑢𝑎𝑙 𝑉𝑜𝑟𝑔

𝑛𝑜𝑟𝑔 = 𝑛𝑡𝑜𝑡𝑎𝑙 − 𝑛𝑎𝑞

4 Remaining
100𝑚𝐿
𝑛𝑎𝑞 = 10𝑔 = 0.105𝑔 unextracted in
100𝑚𝐿 + (8.5 × 25𝑚𝐿) aqueous layer

10𝑔 − 0.105𝑔 = 9.895𝑔 Extracted in combined organic layers

 Determining Volume of Solvent
Given that K = 10, what is the minimum volume of solvent is needed to extract
99.5 % of compound A from 100 mL of water with a single extraction?

𝑛𝑜𝑟𝑔 𝑉𝑎𝑞
𝐾= 𝑛𝑜𝑟𝑔 = 𝑛𝑡𝑜𝑡𝑎𝑙 − 𝑛𝑎𝑞
𝑛𝑎𝑞 𝑉𝑜𝑟𝑔
Substitute
𝑛𝑡𝑜𝑡𝑎𝑙 −𝑛𝑎𝑞 𝑉𝑎𝑞
𝐾= Plug in values
𝑛𝑎𝑞 𝑉𝑜𝑟𝑔
1 − 0.005 100𝑚𝐿
Solve for Vorg 𝑉𝑜𝑟𝑔 =
0.005 10
𝑛𝑡𝑜𝑡𝑎𝑙 −𝑛𝑎𝑞 𝑉𝑎𝑞
𝑉𝑜𝑟𝑔 = = 1990𝑚𝐿
𝑛𝑎𝑞 𝐾
VERY INEFFICIENT
USE MULTIPLE SMALL EXTRACTIONS
 Number of Extractions Needed
Given that K = 10, how many 20 mL extractions are needed to extract 99.5 % of
compound A from 100 mL of water?
Solve for r
𝑉𝑎𝑞
𝑟 𝑛𝑎𝑞
𝑛𝑎𝑞 = 𝑛𝑡𝑜𝑡𝑎𝑙 𝑙𝑜𝑔
𝑛𝑡𝑜𝑡𝑎𝑙
𝑉𝑎𝑞 +𝐾𝑉𝑜𝑟𝑔 𝑟=
𝑉𝑎𝑞
𝑙𝑜𝑔
𝑉𝑎𝑞 + 𝐾𝑉𝑜𝑟𝑔

0.005
𝑙𝑜𝑔 Need only 5 extractions…
1
𝑟= = 4.8 ≈ 5
100𝑚𝐿 100mL total solvent!!!
𝑙𝑜𝑔
100𝑚𝐿 + (10 × 20𝑚𝐿)