Experiment #1:

Purification of Benzoic Acid by Recrystallization

John Edward O. Tanchuco & Carolyn Marie D. Legaspi Section AB2 April 29, 2009

Experiment Objectives
To purify and separate benzoic acid crystals from an impure sample using crystallization. To perform the proper laboratory techniques in recrystallization. To understand the concepts and computations involving purification and recrystallization.

Introduction
Purification
involves the physical separation of contaminants from a sample to produce the desired pure compound. aims to remove by-products and impurities from an impure sample. for liquids, we usually employ distillation but for solids, we use recrystallization.

Introduction
Recrystallization
a common purification method for organic compounds esp. solids the dissolution of the solid with an appropriate solvent at a high temperature & its recrystallization at a low temperature. two types of impurities: (1) more soluble than main component (2) less soluble

Recrystallization Process
An impure solid compound is dissolved in a solvent and crystallizes as the solution cools. Compounds, which are less soluble, will crystallize first. As crystals form, it selects the correct molecules, that fit in the crystal lattice & ignore the wrong molecules, resulting in a

Recrystallization Process
The crystallization process heavily depends on the differences in the solubilities of the desired solutes and the impurities dissolved in the solvent.

Recrystallization Process
Limitations
the process cannot separate pure substances and impurities with the same solubilities in a given solvent. the process is not perfect; it cannot assure a perfectly pure solute, but it does increase its purity. the process is limited to solid solutes.

Recrystallization Solvent
In the ideal setting
the solvent would completely dissolve the compound to be purified at high temperature, usually the boiling point of the solvent, and the compound would be completely insoluble in the solvent at room temperature or at 0oC. and vice versa for the impurity

Recrystallization Solvent
In the real world
In the real world, this will never happen and recrystallization is a technique that has to be practiced and perfected. Regardless of crystallization method, the purity of the solid can be verified by taking the melting point.

Recrystallization Solvent
Common Recrystallization Solvents
solvent formula polarity boiling point (0C) 100 78 65 40 35

water ethanol methanol dichlorome thane diethyl ether

H 2O very polar CH3CH2OH polar CH3OH CH2Cl2 (CH3CH2)2 O polar slightly polar slightly polar

* Note: Properties of a good recrystallization solvent will be elaborated later.

Recrystallization vs. Precipitation

Recrystallization
Rate slow

Precipitation
fast random amorphous solid significant

Formation selective of crystals Shape of crystals pure regular crystals

Amount of negligible impurities

Experimental
Step 1: Mix boiling chip, 100 mg impure benzoic acid, & 2 ml distilled water. Dissolve and heat while constantly swirling.
Erlenmeyer flask benzoic acid solution

hot plate

Discussion
Water is an ideal solvent for benzoic acid.
at 10C, 2.1 g of benzoic acid dissolves in 1000 ml of water. but at 95C, 68g benzoic acid is soluble per 1000 ml of water. this implies that at different temperatures, benzoic acid has an huge solubility difference in water.

Discussion
Constant swirling at a high temperature.
swirling speeds up the dissolution of benzoic acid in water agitation increases the entropy of the system, thus increasing the interaction between benzoic acid and water molecules. the complete dissolution of benzoic acid results to a

Discussion
Adding the boiling chip while at room temperature.
adding the boiling chip at room temperature prevents boiling over. this means that the solution will not spill out, since the boiling chip induces boiling of the mixture.

Experimental
Step 2: Cool the solution. Add activated charcoal. Add a few drops of water. Heat again until observable change is seen.

Discussion
Decolorizing the solution with activated charcoal.
activated charcoal are carbon atoms that are finely separated. these can adsorb impurities (stick to the surface of the substance) from the solution but are quite large to pass through the filter paper. this results to minimization of impurities, and increased purity. WARNING: too much activated carbon could cause the loss of the pure substance.

Experimental
Step 3: Pour the hot solution in the filter syringe and force the liquid through the syringe.benzoic acid
Buchner funnel vacuum(suction)

filtrate

Discussion
First filtration of the solution
activated charcoal used, as well as other impurities, would be separated from the solution and left in the cotton plug. this lessens the impurities in the crystallization process, and increases the purity of the yielded substance.

Discussion
Filtering the solution rapidly.
as filtration is taking place so is the crystallization process. the decrease in temperature causes a decrease in the solubility of the benzoic acid crystals. some of the pure crystals would be separated from the filtrate and would be left as residue. a lesser yield would result if

Experimental
Step 4: Let the mixture cool in the ice bath.

Discussion
Slow cooling in ice bath.
slow cooling makes the crystals arrange finely, thus ensuring correct molecular arrangements/geometry. this helps the crystals form in an undistorted manner and exclude the impurities in crystal formation.

Experimental
Step 5: Collect the crystals on a filter paper. Rinse vial with ice cold water to collect the remaining crystals in it. Use a seed crystal if necessary.

Discussion
Using a seed crystal.
in cases, that crystallization while cooling does not take place, a seed crystal is employed. the seed crystal has the same structure as the pure crystal to be recovered. the seed crystal serves as a source code where the desired solid in the solution begins crystallization.

Discussion
Using a seed crystal.
since the lattice is a perfect fit, the other dissolved crystals would crystallize out as well. impurities would remain dissolved in solution since its structure differs from the seed crystal and cannot fit in the lattice.

Experimental
Step 6: Squeeze excess water from the filter paper. Dry it completely & weigh the filter paper.

Discussion
The filter paper and crystals must be completely dried.
the added mass of water while weighing produces an inaccuracy in the desired data (% recovery) due to the solvent molecules.

Results
% recovery of benzoic acid crystals Weight of impure sample = 100 mg Weight of filter paper = 400 mg Weight of filter paper and benzoic acid = 450 mg Weight of pure crystals = 50mg % recovery: 50mg/100mg x 100% = 50%

Discussion
Not all groups had the same yield even if everyone used 100 mg of the same impure benzoic acid sample. Even if the same bottle was the source of the benzoic acid, the amount of impurities from each group may have varied. In conclusion, the quantity of impurities and crystals recovered in each group varied.

Discussion
Possible error source
Incomplete dissolution of impure sample

Resulting yield
Less yield

Excessive activated chracoal

Less yield
Less yield Less yield Greater yield Less yield Greater yield Less yield

Comparative Group Results

1
2 3 4 5 6 7 8 9

50%

Spilling

38%

Spilling

80%

Minimal spilling

Conclusion
Recrystallization is a laboratory technique used in purification of solids. It is not a perfect process and does not produce an accurate yield. A large amount of impurities with the same solubility as the pure substance is also present, making effective separation difficult.

Guide Questions
Question#1: List the properties that an ideal solvent should have to perform the purification of organic compound by recrystallization technique.

Answer
In the ideal setting
the solvent would completely dissolve the compound to be purified at high temperature, usually the boiling point of the solvent, and the compound would be completely insoluble in the solvent at room temperature or at 0oC. and vice versa for the impurity

Answer
A suitable solvent should be: 1. Soluble at the boiling point of the solvent and slightly soluble at room temperature. (if soluble, hard to separate pure crystals because the molecules interact) 2. The impurities should either dissolve at room temperature or insoluble in the hot solvent so that

Answer
A suitable solvent should be: 3. The solvent should not react since their interaction would result to a lesser yield of pure crystals. 4. The solvent should be volatile enough to be easily removed from the solute/s. This allows rapid drying of the solid compound after it has isolated from the solution.

Guide Questions
Question#2: What advantages does water have as a crystallization solvent?

Answer
exists as a liquid and can be used for a wide temperature range (1C -100C) non-flammable and nonvolatile polar which can easily dissolve molecules esp. polar substances high heat capacity and can dissolve different substances safe and non-toxic compared to other organic

Guide Questions
Question#3: Two students crystallized 10g samples of benzoic acid from water, the first dissolving benzoic acid at 80C and filtering at 10C , the second dissolving at 95C and filtering at 18C .

Calculate the quantity of water each student was required to use and the maximum recovery of benzoic acid possible in each case.

Answer
1st Student: 2nd Student:

@ 80C 10 g = 2.75 g X1 ml 100 ml X1 = 363.6364 ml @ 10C

@ 95C 10 g = 6.80 g X2 ml 100 ml X2 = 147.0588 ml @ 18C

Y1g

= 0.21g

Y2g

= 0.27g

363.63 ml 100ml Y1 = 0.7636 g 10 g 0.7636 g = 9.24 g

147.06 ml 100ml Y2 = 0.3971 g 10 g 0.3971 g = 9.60 g

Guide Questions
Question # 4: A Solid (X) is soluble in water to the extent of 1 g per 100 g of water at room temperature and 10 g per 100 g of water at the boiling point.

Guide Questions
a) How would you purify X from a mixture of 10 g of X with 0.1 g impurity Y, which is completely insoluble in water and 1 g impurity Z having the same solubility characteristics in water as X?

Answer
Dissolve the mixture in 100 g water and heat until boiling (100C). Cool the mixture to room temperature. Then filter to separate impurity Y from the mixture. Add water to the filtrate up to 100ml. Heat the mixture again until boiling until all crystals dissolve. Slowly cool the mixture to room temperature.

Answer
The residue left on the filter paper is the purified X crystals.

The formation of impurity Z is insignificant since it is minimal in quantity (1g) and has a different lattice structure from the solid X structure thus excluding Z in crystal formation.

Guide Question
b) How much pure X could be obtained after one recrystallization from water? ANSWER: 10g 1g x 100% = 90% 10 g Since the solubilities of different solutes are independent of each other, at room temperature, it would be assumed that 1 g of solutes X and Z would dissolve. So, 9 g of pure X solute will crystallize.

Guide Question
c) How much pure X could be obtained after one recrystallization from a mixture of 10g of X with 9 g of Z?

Answer
To retrieve pure solid X crystals from the mixture, all X and Z must be dissolved. The solubilities of X and Z are independent of each other and to dissolve all crystals, solid X is used as basis for it is present in a larger amount. 10g = 1g X = 1000 g water X g 100g

Answer
To ensure that Z doesnt crystallize back, the final amount of water must ensure that solute Z crystals remain dissolved in water under room temperature. This can be done by heating the solution until 900 g water is left. 9g = 1g Y= 900 g water Y g 100g

Answer
The solution is slowly cooled until crystals are formed. Z g = 1g Z= 9 g solid X 900g 100g In 900 g water, 9 g of solutes X and Z are dissolved which means only 1 g of pure solid X can crystallize from the solution.

d) Based on the results obtained, what is suggested about the use of crystallization as a purification technique? ANSWER: The crystallization technique is very inaccurate because it heavily relies on the differences in solubility. Therefore, it is difficult to separate substances with the same solubilities especially when present in the same mixture with significant

THANK YOU!!!
Group 1 Section AB2