Sublimation - Extraction Caffeine from Tea Leaves - Techniques in Organic Chemistry

Caffeine is a bitter, white crystalline xanthine alkaloid that acts as a stimulant drug. 

Caffeine is found in varying quantities in the seeds, leaves, and fruit of some plants, where it acts as a natural pesticide that paralyzes and kills certain insects feeding on the plants. It is most commonly consumed by humans in infusions extracted from the seed of the coffee plant and the leaves of the tea bush.

In humans, caffeine acts as a CNS (central nervous system stimulant), temporarily warding off drowsiness and restoring alertness. It is the world's most widely consumed psychoactive drug, but, unlike many other psychoactive substances, it is both legal and unregulated in nearly all parts of the world. 

Product Name	Serving Size	Caffeine(mg)/serve	Caffeine(mg/L)
Coffee, decaffeinated	207 mL (7.0 US fl oz)	5–15	24–72
Coffee, espresso	44–60 mL (1.5–2.0 US fl oz)	100	1,691–2,254
Tea – black, green, and other types, – steeped for 3 min.	177 millilitres (6.0 US fl oz)	22–74	124–416
Guayakí yerba mate (loose leaf)	6 g (200 US fl oz)	85	approx. 358
Coca-Cola Classic	355 mL (12.0 US fl oz)	34	96

 References from Wikipedia

 

Chemical:
Dichloromethane: 20mL

Sodium carbonate monohydrate: ~7g

Tea leaf (High Mountain Oolong Tea): 10.00g

Magnesium sulfate anhydrous: Some

Procedure:

Extraction of Crude Caffeine from Tea Leaves

1.      Weight about 10g of tea leaves (precise to 0.01g).

 

2.      Dissolve sodium carbonate in 50mL water.

3.      Pour the solution onto tea leaves

4.      Boil the cup of tea for 20~30 minutes.

 At the beginning of heating

5.      Cool the solution to below 20℃ in ice bath

6.      Decant the thick, dark solution into a separatory funnel.

 Very Thick Tea

7.      Add another 10mL water to wash the tea leaves and also decant into the separatory funnel.

8.      Add 10mL dichloromethane into the separatory funnel to extract caffeine from aqueous layer.

 

9.      Add another 10mL dichloromethane to extract caffeine again and combine it with the other extraction.

10.  Pour the dichloromethane solution in to a flask.

 We can clearly see, there are still some aqueous in the solution

11.  Add enough  magnesium sulfate to remove water from the organic solvent.

We added some magnesium sulfate to remove water

12. Separate the desiccant(magnesium sulfate) from the solution.

 Use a pill of cotton and a funnel could remove desiccant faster than a filter paper

 

13.  Use a rotary to evaporate all the solvent dichloromethane.

14.  Now we get the crude caffeine

The sublimation of crude caffeine

1.      Take our crude caffeine in to a flask

2.      Put on a stop with a hole with a test tube and the test tube is filled with iced water.

3.      Put the apparatus onto a hot plate and control the surface temperature around 180℃(because the sublimation point of caffeine is 178℃ under an atmosphere)

4.      Keep the water in the test tube cold.

 Caffeine start deposition on a cold surface(the test tube)

5.      After no longer substance sublimating, take the apparatus from the hot plate.

6.      Collect all the sublimated caffeine from the vessel

 Collect the caffeine from the test tube

 Total caffeine which was purified from sublimation

 Analysis

Name	Unit
Weight of Tea Leaves (g)	10.140
Weight of Crude Caffeine (g)	0.050
Weight of Sublimated Caffeine (g)	0.020
Crude Caffeine / Tea Leaves (g/g)	0.005
Sublimated Caffeine / Tea Leaves (g/g)	0.002

The Systematic Analysis of Cation Group 3 - The Basic Hydrogen Sulfide Group - Al+++, Cr+++, Fe+++, Fe++, Mn++, Co++, Ni++, Zn++

 Cation Group 3 – The Basic Hydrogen Sulfide Group
 
The eight inos of this group are precipitated as sulfides or hydroxides by a combination of hydrogen sulfide or thioacetamide with an ammonia-ammonium chloride buffer. None of these ions form chlorides, sulfides, or hydroxides sufficiently insoluble to precipitate from a solution that is 0.1 to 0.3 M in hydrochloric acid.

Al+++, Cr+++, Fe+++, Fe++, Mn++, Co++, Ni++, Zn++

Outline

Original Sample:

 

Precipitate of the Group:
Dilute the sample to volume is about 2 mL.
Add 6 drops 6M NH₄Cl ; 15M NH₃ . Add 4 drops TA solution. And boil it for 5 minutes.

 Precipitation formed after added TA solution

Centrifuge the solution, and use NH₄NO₄ solution to wash the precipitation. The solution is for the test of Cation Group 4. Separate the solution and precipitation.

 

Add 10 drops 16M HNO₃ to dissolve the precipitation. Centrifuge the solution and discard precipitation.

Precipitation is floating on hot nitric acid solution

Solution 1

Use gentle fire to vapor it with 15 drops 15M nitric acid (do not heat it to dry). Repeat the step three times.

Drop out about 1~2 drops of Solution 1 to do Mn Test 1

Mn Test 1

Dilute 1 drop of sample with several drops of water. Add some NaBiO_3.

The Right One is Mn Test 1

Boil Solution 1, and add some KClO₃ (to raise the oxidation state of manganese) and some nitric acid until black precipitation forms.

Black precipitation at the crucible with some nitric acid

Wash with some water, centrifuge the solution and separate solution from precipitation.
And label the solution as solution 2, precipitation as precipitation 2.

Yellow solution show the sample contain Fe+++

Mn Test 2



Add 6 drops HNO₃ 16M and 1 drop H₂O₂ into the precipitation 2. And then add NaBiO₃ some powder.
 

The Left One is the Mn test 2

Add 10 drops 6M NaOH_(aq) into the Solution 2. And 1 drop 3% H2O2. Put it into hot bath for 5 minutes. Centrifuge and wash precipitation with 10 drops water and 1~2 drops 6M NaOH solution. Collect  all liquids and centrifuge them together. Separate solution from precipitation and label solution as solution 3, precipitation as precipitation 3.

Hydroxide precipitation formed

Precipitation 3

Add 6 drops HCl 12M to dissolve the precipitation 3 and dilute it with 10 drops water. Divide the solution between two test tubes. One for Ni test and one for Fe, Co test.

Fe Test

Add some NH₄SCN in to one of the test tube to react with the solution. A blood red color show the existence of of Fe.

Iron ion formed complex with thiocyanate ion

Add some NaF powder in to the solution to quench out the color of the complex and thiocynate ion.

Fluoride ion would react with iron ion and

 form insoluble salt iron fluoride precipitation

Co Test

And then add some drops ammonium thiocyanate solution of ethanol-ether into the test tube. Cobalt ion would form a greenish color complex in the organic layer(ethanol-ether layer).

A greenish color shows the existence of Co ion

Ni test

Take another solution sample, and add some ammonia solution to alkalize the solution.
Add drops DMG(dimethylglyoxime) solution. The solution turn red shows the existence of nickel ion.

Looks like grape fruit juice color shows the existence of Ni ion

Solution 3

Divide solution 3 into three parts, one for Cr test, one for Al test and one for Zn test.

Cr test



Add some acetic acid and drops lead acetate into one part of the solution.Yellow precipitation form. It would be PbCrO₄ .

Yellow precipitation would be PbCrO₄

Ensure the yellow precipitation is lead chromate, centrifuge the solution to separate the precipitation from the solution.Add 1 drop 6M HNO₃ and 1 drop 3% H₂O₂ into precipitation.

A blue color would form immediately and vanish in a second. It is supposed to be CrO₅ .

It is one kind of a very unstable state of chromium oxide.

 Blue color forms and vanishes just in seconds

Acidify the other two parts of solution with 6M HCl add 5 drops 6M NH₄Cl and NH₃ to basic. Centrifuge it and separate the solution from the precipitation.

 

Aluminum hydroxide form a white precipitation

Al Test

Dissolve the precipitation in 6M HCl solution, add 2 drops aluminon agent and NH₄OAc .

A cranberry color formed, it show the existence of Al ion

Zn Test

Add 2~3 drops BaCl₂ in to the solution, centrifuge it. Discard precipitation. Add some drops of TA solution and centrifuge it to take out the precipitation. Dissolve  in HNO₃ and add some drops NaOH. Test the solution by dithizone paper.

Dithizone would form complex with Zn ions, 

the complex looks like cranberry red

References:

1. Qualitative Analysis and Electrolytic Solution
2. Introduction to Semimicro Qualitative Analysis (8 ed.)