Experiment 10 ONLINE TECHNIQUES

Extraction is process where a substance is isolated from a mixture by chemical, physical, or mechanical means.

i. Distillation
ii. Sublimation
iii. Filtration
iv. Preparative column chromatography.

We use liquid-liquid extractions (i.e. transfer a dissolved substance (solute) from one solvent to another).

For example, we want to isolate an organic compound as a dry solid from aqueous solution.

Inproper Technique Proper Technique

Boil off water by heating solution to 100oC, Transfer compound to a low-boiling, organic
but dissolved organic compound may be solvent (e.g. dichloromethane) through liquid-
thermally unstable and decompose at water’s liquid extraction. Then, boil dichloromethane
b.p.! at much lower temp (e.g. 40oC) ensuring
organic compound does not decompose.

Result is dry and chemically intact solid!

Q: The above procedure would not be effective (or necessary) if the compound to be purified from an aqueous
solution decomposed at a [higher] temperature and had [lower] solubility in dichloromethane.

Liquid-liquid extractions used when can change solvent. It can also separate components of a mixture (i.e.
according to different solubilities in different solvents).

Conditions for liquid-liquid extraction (i.e. between water and dichloromethane)

i. Solute dissolved in water must also be soluble in dichloromethane.

ii. Compound must be more soluble in dichloromethane than in water (i.e. true for many organic compounds).
iii. Water and dichloromethane must be immiscible (i.e. incapable of forming a homogenous mixture).

Separating Mixtures

Say compound being transferred into dichloromethane from water is initially mixed with another solute in water.

If other solute in water is not soluble in dichloromethane, then extraction separates two solutes (i.e. as solutes
migrate to/remain in solvent in which they are most soluble; partitioning).

i. One moves into dichloromethane.

ii. Other stays in water.

So, less dense solution floats on top of more dense one without mixing (i.e. immiscibility).

(Sepratory funnels in extractions designed to facilitate separations of liquid layers).

Proper Experimental Technique

Liquid-liquid extraction performed with a separatory funnel.

Steps

i. Place a clean separatory funnel into a ring clamp as shown in the picture. You might have to place a clay
triangle over the ring and seat the funnel in the triangle if the diameter of the ring is larger than that of the
funnel. Close the stopcock of the funnel.
ii. Pour the solution that is to be extracted (i.e. ensure solution at room temperature).
iii. Pour in extracting solvent, and seal funnel using stopper.
iv. Carefully remove separatory funnel from ring clamp, and turn it upside down. Keep one hand holding
stopper in!
v. Open stopcock to vent the solvent vapour-pressure inside. DO NOT point the funnel stem at anyone
during the venting process, as solvent droplets might blast into their face!
vi. Close stopcock, and rock funnel back and forth for a few seconds. Do not rock too vigorously, as an
emulsion will form.
vii. Vent the pressure (i.e. hiss). Close stopcock, and rock funnel again for a few seconds.
viii. Repeat vii x5.
ix. Return separatory funnel to ring clamp. Let it sit undisturbed for a minute as the two solvent phases
separate. If an emulsion forms (i.e. a thick interface layer of bubbles), stir the contents of the funnel with a
stirring rod.
x. Place a clean, dry beaker under the funnel stem.
xi. Remove the stopper and carefully open the stopcock to drain the lower solvent phase into the beaker. Do
not let any of the interface bubble-layer leave the separatory funnel!

Partition Co-Efficients and Phase Separation

Two solutes are slightly soluble in both solvents (i.e. so never have 100% of a solute being transferred from one
solvent into another).

Goal is to extract the largest possible amount of solute into a new solvent. For example,

2.18 g caffeine dissolves in 100 mL of water. 18.2 g dissolves in 100 mL of dichloromethane.

(Both measurements at same temperature (i.e. Ksp depends on temperature).

Partition co-efficient for caffeine = (18.2 g/100 mL)/(2.18g/100mL) = 8.35. (Ratio of relative solubility). Changes
with temperature!

Say we have 50 mL cola (20 mg caffeine), and 30 mL dichloromethane. We can...

i. Carry out a single dichloromethane wash of the aqueous solution, using all 30 mL of dichloromethane at
once.
ii. Perform [] sequential dichloromethane washes of the aqueous solution, using [] portions of []
dichloromethane each. (Three washes for optimal caffeine extracted!)
Say x mg caffine (i.e. from starting 20 mg) migrates from cola layer into dichloromethane. So, 20 – x mg in cola
layer.

We have (1) relative volumes of layers, and (2) partition co-efficient = 8.35. So, can solve for x!

At 25oC; 8.35 = (mg caffine / mL dichloromethane) / (mg caffeine / mL water). i.e.

(x mg caffeine / volume of CH2Cl2) / ((20 – x) mg caffeine / volume of cola sample in mL).

Extraction Flowchart (Summary)

i. Extract organic solution x3.

ii. Combine layers.
iii. Evaporate solvent (i.e. caffine).
iv. Determine purity of caffeine.

Q: What experimental condition could be changed that would result in an even greater extraction percentage, yet
not increase the amount of time spend performing the extractions?

Melting Point Analysis

Melting point is a characteristic physical property of a substance.

Melting point analysis identifies chemical substances (i.e. m.p measured, compared to literature values); amount
needed is small.

Melting point can also provide information about purity of a sample (i.e. impure substances melt at lower
temperature than pure compound, and over wider range of temperatures).

[See Q].

When a substance melts, an eqm is established between its solid and liquid form, which is gradually shifted to
favour the liquid form as temperature increases.

[See Q].
Crystalline Solids

Most laboratory solids (i.e. organic or inorganic) are crystalline solids. These have molecules (e.g. for solids like
caffeine), or repeating clusters of ions (i.e. for solids like CuSO4) arranged in a regular, tightly packed repeating
crystal lattice.

This lattice is held together by various intermolecular forces (i.e. due to chemical nature of solid).

Forces are disrupted when substance melts (i.e. which requires energy input). Results in an elevated temperature.

Stronger forces = higher m.p

For ionic solids, attractive forces are mostly electrostatic (i.e. particles with opposing charges alternate in lattice).
Electrostatic forces are very strong; lead to melting points that are 100oC+.

Ionic solids rarely analyzed by melting point because of very high temperatures necessary.

For molecular solids (i.e. neutral), various dipole forces hold solids together. Dipole forces are weaker version of
electrostatic forces in ionic solids; they are incomplete charges (i.e. due to polar molecules).

Different atoms in a given molecule have different affinities for negatively charged electrons that form a cloud
around the atomic nuclei.

[Review electronegativity]. Note that atoms with higher electronegativities are more –ve charged; distribution of
charge (i.e. charged are aligned so that partially –ve atom closest to partially +ve atom) creates attractive forces
between molecules that hold them together.

Molecular solids are used in melting point analysis!

Therefore, foreign substances (i.e. impurities) affect melting point, as they disrupt the repeating pattern of forces
(i.e. greater variation in intermolecular forces) that holds the solid together (i.e. smaller amount of energy is
required to melt).

Proper Experimental Technique

i. Place a small pile of the solid substance to be analyzed on a watch glass.

ii. Dip open end of the melting point capillary tube into the solid so that 3-4 mm of sample adheres to bottom
end of tube.
iii. Invert tube so that open end is pointing upwards, and gently tap the closed end of the tube against a hard
surface. Causes solid matter to fall into the closed end of the tube.
iv. (If sample still stuck on walls of tube, shake it loose by dropping capillary pipet down 2 foot-long glass
dropping pipe. Stand dropping pipe up vertically on benchtop, and drop pipet (i.e. closed end first) through
dropping pipe.
v. After (i) – (iii), heat sample in melting point apparatus. Record temperature when first trace of liquid
appears, and temperature when last trace of solid disappears.

Melting Point Apparatus

 Electrical device with thermometer, magnifying glass, and heating block (i.e. with drilled hole to allow a
melting point capillary tube to be inserted). (Can heat to >500oC).
 Use Gallenkamp apparatus in labs (i.e. load x3 tubes at once).
  Two switches and a dial that control apparatus
o One switch turns primary boost heater on and off.
 Heater rapidly increases temperature of heating block.
 Heating power cannot be varied.
o Second switch turns secondary heater on and off; heating power controlled by dial.

Using the Melting Point Apparatus

Melting point determinations always performed twice.

 First trial is test run to determine when and how to make a detailed and more careful observation of the
melting in the second trial.

In a real research setting, leave all heating settings at a maximum to rapidly determine approximate melting point
of sample. Then, let apparatus cool down to at least 40oC below m.p., then insert second sample into device. In
second trial, only use secondary heater to increase temperature at a much slower, precisely controlled rate.

Steps

i. Turn off both heater switches, and set dial to zero. Ensure apparatus doesn’t exceed 50oC.
ii. Insert melting point capillary tube (i.e. packed with sample).
iii. Turn on “heater and lamp” switch . Check view of sample through magnifying glass.
iv. Set power dial to “10”.
v. Switch on “boost heater”.
vi. When the thermometer reaches 180oC, turn off “boost” and set power level to “6”. Temperature will drop,
but should climb again promptly. Increase power if temperature doesn’t climb!
vii. Switch off power and discard the melting point tube into the provided 400 mL broken glass waste beaker.

Q: Why not just record the average melting point from the range (i.e. why is magnitude of range important)?

Vacuum Sublimation

Sublimation is a separation technique used to purify a solid chemical substance; vacuum

= low pressures.

i. Solid heated in a flask under vacuum.

ii. Solid sublimes directly into a gas.
iii. Gas is condensed on a cold surface (I.e. causes solid to re-form).
a. Impurities (i.e. heavier molecular weight) left behind on bottom of flask if
impurities have vapour pressure (i.e. related to boiling point) different
from desired product (i.e. if not, use other separation techniques.
iv. Solid scraped off cold surface for further reactions or analysis.
Why doesn’t solid turn into liquid?

So, we carry out sublimation at lower pressures (i.e. using a vacuum).

Also, substances sublime at lower temperatures as pressures are lowered; so lowering pressure reduces risk that a
substance will be destroyed by intense heat during a sublimation.

To convert clean vapours back into a solid, reverse “0.01 atm” arrow.

Cold surface (i.e. outside of test-tube filled with ice on inside) recovers solid, but impurities left behind on hot
surface.

Particles in vapour phase strike cold surface, cool, return to solid phase (i.e. so purification is complete!).

Q: Not all of the sublimed particles strike the cold surface and return to the solid phase. There is a significant
likelihood that some will escape the system altogether. How is the possible? Think of apparatus.

Steps

i. Place solid chemical inside filter flask using a metal spatula. Seal mouth of filter flask with stopper and
cold finger.
ii. Turn on water tap completely to start vacuum, and carefully fill cold finger with mixture of crushed ice and
water.
iii. Turn on hotplate to “4”. Turn off after all solid has sublimed (i.e. 5-10 mins).
iv. Remove hotplate from underneath sublimation apparatus.
v. Leave flask to cool for 15 mins with water pump still on.
vi. DO NOT TURN OFF WATER PUMP UNTIL VACUUM PRESSURE IS RELEASED.
a. If pressure not released, water will be sucked into hot filter flask (i.e. steam explosion of apparatus).
vii. After filter flask cooled down, “break vacuum” by separating two halves of white plastic quick-disconnect
joints along hose.
viii. Turn off water pump, then carefully remove cold finger from filter flask, and scrape sublimed pure product
into a container.

Q: Is vacuum sublimation, as described, a quantitative technique? Can you get four significant figure accuracy for
the yield of a substance by performing the above procedure?