Experiment 2: Crystallization

Abstract:
Crystals are solid body with plane faces in which atoms are arranged in an
orderly repetitive array. Crystallization is a process where crystal structure are
obtained with high degree of purity even when obtained from a relatively
impure solution. The process of formation of crystals by cooling a saturated
solution is called solution crystallization. When the concentration of a liquid
solution is increased (by evaporating/by cooling or both), the solution
gradually reaches the saturation level and then becomes supersaturated. The
supersaturation in a solution provides the driving force for the transport of the
solute from the bulk of the solution to the crystal surface (seed). The solute
molecule gets oriented and integrate into crystal lattice.

Aim:
To determine the yield of benzoic acid crystals using the process of crystallization.

Introduction:
Crystallization is an important operation in processing as a method of both
purification and of providing crystalline material in a desired size range. In a crystal
the constituent molecules, ions or atoms are arranged in a regular manner with the
result that the crystal shape is independent of size and if a crystal grows each of the
faces develops in a regular manner.

Crystallization is the process where a solid separates from the solution. A saturated
solution the solute is altered by either cooling, evaporation of solvent, or addition of
another substance so that the ability of the solvent to dissolve the solute is lessened,
and a fraction of the solute forms a solid phase, which may be removed from the
mixture. Crystallization is the formation of solid particles within a homogenous
phase. Its wide use has a twofold basis a crystal formed from an impure solution is
itself pure and crystallization affords a practical method of obtaining pure chemical
substance in a satisfactory condition for packing and storing. This operation involves
both heat and mass transfer.
The simplest and cheapest type of crystallization consists of an open tank/vessel,
which can be used either as an evaporative or as a cooling crystalline. In batch
crystallization, process the solvent evaporated until the concentration has reached
the required value, and transfer of sensible heat to the surroundings and
evaporation at the free surface then effects cooling. The solution cools slowly and
large crystals are therefore obtained through generally they are uneven because the
nucleation is not controlled in anyway.

The yield of crystals produced by a given cooling may be estimated from the
concentration of the initial solution and solubility at the final temperature allowing
for any evaporation by making solvent and solute balances as follows.

For the solvent, usually water the initial solvent present is equal to the sum of the
final solvent in the mother liquor the water of crystallization within the crystals and
any water evaporated,
y∗R−1
W 1=W 2 + +W 1 E
R

Where W1 and W2 are the initial and final masses of solvent in the liquor, y is the
yield of crystals, R is the ratio (molecular mass of hydrate/ molecular mass of
anhydrous salt) and E is the ratio (mass of solvent evaporated/mass of solvent in the
initial solution).
For The solute
W1C1 = W2C2 + y/R

Where Cl and C2 are the initial and final concentration of the solution expressed as
(mass of anhydrous salt/mass of solvent).

Substituting for W2, we get yield as

R W 1 (C 1−C2 ( 1−E ))
y=
1−C 2( R−1)
Batch crystallization is characterized by the fact the system is always in the unsteady
state. The initial super saturation at which crystallization starts will drop quickly from
relatively high value to the saturation value. If crystal growth is to continue, the
solution must be maintained in the meta-stable region. Therefore, the cooling must
continue and the batch temperature must continue to drop during the growth
period. In batch crystallization, it is comparatively easy to penetrate the labile zone
producing a fine mass of fine crystals. By using controlled seeding, the solution will
not become labile there by aiding crystal growth.

Utilities Required:
Distilled water, benzoic acid, thermometer, glass rod, hotplate, filter paper

Procedure:
1. Hot plate is used to heat the solution to the desired temperature. Glass rod
for stirring, thermometer for temperature measurement.
2. Take a known quantity of distilled water (250 ml) in a flask and heat it to 40°C
on a hot plate.
3. Keep on adding the weighted amount of benzoic acid with simultaneous
stirring by a glass rod, until benzoic acid stop dissolving. Note down the total
amount of benzoic acid that was dissolved.
4. Now remove the flask from the hot plate and allow it to cool.
5. Put 0.2 gm benzoic acid in the crystallizer when the temperature reduces by
5°C, for seeding.
6. After formulation of crystal filter the solution and measure, the amount of
mother liquor obtained and titrate the solution with 0.1 N NaOH.
7. Collect all the crystal from the mesh on a filter paper wash it and put it in oven
for drying.
8. Weigh the dried crystal obtained

Observation:
 Amount of benzoic acid dissolve in feed = 2 gm
 Volume of feed = 250 mL
 Burette reading for titration of 10 mL feed solution against 0.1 NaOH = 3.3 mL
 Volume of filtrate = 217 mL
 Weight of filter paper = 1.271 gm
 Final weight of filter paper (with crystals on drying) = 2.093 gm
Calculations:
Initial Normality of NaOH = 0.1N

N1.V1 = N2.V2 (1) NaOH (2) Benzoic acid

N2 = 0.01 x 3.3 = 0.033 N

Strength = 0.033 x 122.12 = 4.029 g L-1 = 1.00749 g/250mL = 0.875 g/217mL

Crystals formed = (2.411 –1.271) gm = 1.14 gm

weight of crystals obtained

Percentage efficiency of crystallization = ∗100 %
amount of benzoic acid ∈the feed
1.14
= ∗100 = 57 %
2

Results and conclusion:

The percentage efficiency of crystallization is 57 %.
The strength (0.875 g/217mL) calculated above is coherent with the literature values
of saturation at 25°C of 0.86 g/250mL solubility of benzoic acid indicating that the
complete formation of crystals have taken place and that the mother liquor only has
benzoic acid in the saturation range of 25°C. The percentage of benzoic acid
obtained from crystallization is moderate. This is because benzoic acid has high
solubility in high water but low solubility in cold water. This is because the carboxylic
acid group is polar however the bulk of the acid is non-polar. As the temperature is
increased there is more energy present to overcome the weak hydrogen bonding
between water and weak Van der Waal’s bonds are formed between benzoic acid
and water.

Precautions:
 Do not touch KOH pellets with Bare hands as it is corrosive
 Handle all glassware carefully