Unit – 6B

Heating under reflux:

It is used when the reaction is slow and one of the reactants is volatile.
The organic vapours that boil off as the reaction mixture is heated are condensed and
flow back into the reaction vessel.
As most organic compounds are flammable, it is safer to heat the mixture using an
electric heater or a water bath rather than direct heating.


This is used to remove a volatile substance from a mixture containing non-volatile
inorganic species, such as acid or alkali.
This can also be carried out to separate two volatile organic substances present in a
homogeneous mixture only when there is a large enough difference in the boiling
temperature of the organic substances.
The product must not decompose at the boiling temperature
The mixture is carefully heated and the vapour that comes over at ± 2ºC of the boiling
temperature (obtained from a data booklet) of the particular substance is condensed
and collected.

Prepared By Adnan Chowdhury

Page 20

The organic compound is separated by adding a suitable organic solvent which dissolves the organic compound but not the inorganic one. The flask should never be heated with a naked flame. The organic compound and Prepared By Adnan Chowdhury Page 21 . Gloves must be worn when corrosive substances are used. If there is not. liquid around. and often corrosive. spraying hot. it is particularly useful for obtaining a substance that would decompose at its boiling point. This is because almost all organic substances are flammable and if the liquid being heated were to spill over or the flask to crack. pressure will build up in the apparatus. flammable. Solvent Extraction:    An organic product can often be separated from inorganic substances by solvent extraction.Unit – 6B Steam Distillation:   It is used to extract a volatile substance that is insoluble in water from a reaction mixture that contains an immiscible liquid as well as a solution. If the mixture is being heated under reflux or distilled. The thermometer bulb must be placed adjacent to the mouth of the joint at the neck of round bottom flask. which will then fly apart. a fire would result. This is useful when the components of a mixture have similar boiling temperatures and fractional distillation is not possible. poisonous (toxic) or irritant. there must be some outlet to the air. Safety Precautions:      Distillation (simple or steam) and heating under reflux must be carried out in a fume cupboard if the vapour of one of the reactants or products is harmful. Such substances are must always be handled with care.

 The filtrate is allowed to cool and the crystals of the pure solid appears. This removes any unreacted sodium salts and any soluble organic substances. The pressure must be released from time to time to let out the carbon dioxide. usually with lumps of anhydrous calcium chloride or calcium oxide or silica gel.Unit – 6B the solvent should have a large enough difference in boiling temperature so that they can be later separated by distillation. This removes any insoluble impurities.  A suitable solvent is chosen in which the solid is soluble when hot and almost insoluble at room temperature. Purification of a liquid that is insoluble in water: The product is distilled out of the reaction mixture and the following processes are carried out:  The distillate is washed with sodium carbonate or sodium hydrogen carbonate solution in a separating funnel. Less dense liquid More dense liquid  The aqueous layer is discarded and the organic layer is dried. This removes any acidic impurities. Prepared By Adnan Chowdhury Page 22 .  The solution is filtered through a pre-heated glass filter funnel fitted with a fluted paper. CO32-(aq) + 2H+(aq)  CO2(g) + H2O(l) HCO3-(aq) + H+(aq)  CO2(g) + H2O(l)  The aqueous layer is discarded and the organic layer is washed with water. Solid potassium hydroxide is used to dry amines and alcohols as they forms complex ions with calcium chloride Purification of a solid by Recrystallisation: The solid is filtered off from the reaction mixture and purified by recrystallisation. Minimum volume is used to get a saturated solution. This washing is repeated until no more fizzing is seen.  The solid is dissolved in minimum amount of hot solvent. such as ethanol.

The thermometer is placed into a bath of liquid. Prepared By Adnan Chowdhury Page 23 . The liquid must boil at a higher temperature than the melting temperature of the solid being tested. The temperature is noted when the solid melts.  The solid is washed with a little cold solvent in order to remove any remaining insoluble impurities.Unit – 6B  Then filtration is carried out again using a Buchner funnel under reduced pressure. Using filter papers will reduce the yield as some of the solids will get stick to the papers. This removes any soluble impurities. The solid is then dried either between packs of filter paper or else a vacuum desiccator or an electric oven. Slowly the liquid bath is heated with constant stirring and solid in the capillary tube is observed.  Melting Point Determination: Method 1:    Some of the pure solid is inserted into a capillary tube and then the tube is attached open end upwards to a thermometer with a rubber band.

a thermometer and a stirrer are placed in the molten solid and boiling tube is removed from the liquid bath. The melting temperature is the mean of these two values.Unit – 6B Method 2:      The solid is placed in a boiling tube. stirring the whole time. The melting temperature is then recorded. and the temperature increased slowly until it melts. Method 3:  The sample is placed in a capillary tube. and the temperature is recorded when the first crystal of solid appears. The molten substance is allowed to cool. The boiling tube is heated in a beaker of hot liquid (water if the solid melts below 100ºC) When the solid melts. Prepared By Adnan Chowdhury Page 24 .

The average of these two temperatures is the boiling of the liquid. Sufficient time is needed to be allowed. but there will be rapid rise and fall in temperature. Oil can be used. Impurities and variation in atmospheric pressure. Averaging these two temperatures cancels out this error Note:  Melting and boiling point determinations are used to identify a substance. It is difficult to judge the flow of bubbles. Both temperatures are slightly inaccurate because there is a time lag before the thermometer can register the boiling temperature. so temperature of liquid is different from that recorded in the thermometer. alter the boiling point. the temperature of the water bath is noted and the heating process is stopped. The beaker of water is allowed to cool. with its open end below the surface. 3.Unit – 6B Boiling Point Determination:        A small amount of the test liquid is placed in an ignition tube and it is attached to a thermometer using a rubber band. stirring continuously. The water is heated slowly. The melting and boiling point are determined and checked with a data booklet. 2. 4. Prepared By Adnan Chowdhury Page 25 .  There are many problems with the boiling temperature method: 1. stirring all the time. An empty capillary tube is placed in the liquid. Water is a poor conductor of heat. When the stream of bubbles coming out of the capillary tube is rapid and continuous. The thermometer is clamped in the beaker of water. The temperature of the water bath is noted when bubbles stop coming out of the capillary tube and liquid begins to suck back to the capillary tube. The boiling points of similar substances are often quite close together and can differ by less than the experimental errors. in case of water to distribute heat equally and reach equilibrium temperature.

Automatic magnetic stirrers can be used. For this reason. Immediately the test sample is stirred with thermometer and a stop watch is turned on. 5. so temperature of solid is different to that on the thermometer. The temperature is recorded at regular intervals of time (every 30 seconds interval for 7 minutes). Oil can be used as a medium. Spirit lamp can be used or the intensity of Bunsen burner flame can be lowered. Solid may be damped or impure. Heating is too rapid. heating is stopped. When the solid completely melts. the intensity of flame of Bunsen burner can be lowered or spirit lamp can be used so heating can be slowed down. The water bath continued is heating. Prepared By Adnan Chowdhury Page 26 . so it is difficult to control the rise of temperature. Stirring is not enough for equal heat distribution. When the solid begins to melt the thermometer is placed in the tube. Insufficient stirring. It is difficult to see solid and thermometer together. The boiling tube containing the test sample is placed in this beaker. The experiment should be repeated until consistent values are obtained. 6. This is called the cooling curve. and the melted solid is stirred. The measurement of boiling point is not very reliable compared to melting point. Heating is too rapid. Automatic magnetic stirrer can be used for uniform heat distribution. A graph is plotted temperature against time. 4. Disadvantages and improvements of melting point determination: 1. The second beaker is left alone on the bench. One beaker is arranged on a tripod and gauze. 2.Unit – 6B   5. Water is a poor conductor. 3. The water in the beaker on the tripod and gauze is heated. Freezing Point Determination:      Two beakers are filled with water. The boiling tube containing the test sample is transferred to the second beaker containing cold water. Solid can be dried by heating inside oven and purified.

gloves when handling corrosive liquids. Doing a reaction in a fume cupboard – thus removing harmful vapours from the work area. Using specific protective clothing – e. and the risk of spillage is reduced. More accurate thermometer can be used.Unit – 6B Note:   The method may not be accurate due to rapid cooling. Types of Hazards:       Toxicity Absorption through the skin Irritation if inhaled Corrosive compounds High flammability Carcinogenic compounds Risks can be reduced by:       Using less material – the reaction is easier to contain and to control. 2. still a hazard but a much reduced one. Prepared By Adnan Chowdhury Page 27 . Risk is the chance that a substance or activity will cause harm. Reducing the temperature at which the procedure is carried out – thus slowing the reaction and reducing the risk of overheating and too many fumes being produced. Improvements: 1. Using lower concentrations of solutions – diluted corrosive solutions can become irritants. Hazards and Risks:   Hazard is the potential of a substance or activity to do harm. Changing the materials used – less hazardous material may not react as quickly or give as much as product.  Handling losses during transfer and purification. but they will allow the same reaction to be studied.g. Slowly cooling in air instead of water. Yield: Yields are less than 100 percent because of:  Competing / side reactions.