BKF3731 Unit Operation Laboratory

SEMESTER II SESSION 2021/2022

CRYSTALLIZATION

Saunthariya A/P Murili, Reveka A/P Rajenderan, Goh Hui Jun, Tan Jing Shi, Gan Ming Xuan
Section 03, Group 03
Dr. Nurul Aini Binti Mohamed Razali
Department of Chemical Engineering, College of Engineering
Universiti Malaysia Pahang, 26300 Gambang, Pahang, MALAYSIA.

ABSTRACT
Crystallization is the formation of solid particles from a homogenous solution. The solution is typically
cooled until the solute concentration exceeds its solubility at that temperature, at which time pure solute
crystals form. The goal of this experiment is to use the Van't Hoff Equation to calculate the dissolving
enthalpy and entropy of Epsom salt (MgSO4) in ethanol, acetone, and water. The crystal structure of
Epsom salt (MgSO4), sugar, and copper sulphate in water is then investigated in this experiment. Finally,
applying crash and natural cooling crystallization, this experiment investigates the recrystallization of
Epsom salt. This experiment is divided into three parts: Parts A, B, and C. Part A deals with the enthalpy
and entropy of Epsom salt dissolution. At temperatures of 40°C, 45°C, and 50°C, Epsom salt was
dissolved to excess in acetone, ethanol, and water. The solutions were then collected and weighed in three
labelled crucibles. The crucibles were dried in the furnace and their dry weight was calculated. Part B had
three distinct crystals: sugar, copper sulphate, and Epsom salt. These three crystals were dissolved in
water until they were completely dissolved at 50 °C. Part C compared crash cooling crystallization to
natural cooling crystallization. Excess Epsom salt was dissolved in water at 55 °C. After that, the saturated
solutions were cooled using both ice bath cooling and natural cooling. Part A results show that the
solubility of Epsom salt was proportional to the temperature. This is because the kinetic energy of the
solvent molecules increases with temperature, thus breaking apart the intermolecular attraction that holds
the molecules together. Part B's results may be stated as follows: the lower the solubility, the higher the
tendency of the component to crystalize. Part C’s results show that the rate of crystallization in ice bath
cooling is quicker than in natural cooling.

Keywords: crystallization; crash cooling; Epsom salt; ice bath cooling; natural cooling.

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1. Introduction
Crystallization can be defined as a chemical phase change process in which a chemical species is
formed in a crystal form from a solution which is in homogenous state. More specifically, crystallization
is a process to lessen the energetic state of an atoms, molecules, or ions by arrange the atoms, molecules,
or ions to form a clear cut, rigid crystal lattice (Mettler Toledo, 2017). A very simple example that occur
naturally in our life is the natural phenomena in which the formation of snow from water vapor contained
in the air during winter season. Crystal solid is formed from asolution that in homogenous phase. The
solution usually in a very concentrated stage and the solution is cooled down until a certain temperature
(Syrris, 2020). As a certain amount of solvent only can accompany solute concentration that are equal to
the solubility of solute particles inside a solvent in a certain temperature. So, when cooling process occur,
the temperature of the solution decreased as in result, the solute concentration in the solvent become
higher than the solubility of the solute in solvent at that temperature. Hence, the solute particles will be
separated from the solution and form a crystal solid particle that contain almost pure solute.

Crystallization is a very wide-ranging used technologies in the separation and purification in many of the
industries nowadays. Every chemical process that will produce an end product with solid state surely
consist at least a crystallization step in the whole unit operation, in any way like purification of the
product, intermediary separation or removal of the subproduct. The Van't Hoff equation is used to
calculate the enthalpy and entropy of dissolving solute in three different solvents: acetone, ethanol, and
water. This equation descripts the relationship between temperature and a solid's solubility. The following
equation can be used to express the relationship, where Δ𝐻𝑑 is the dissolution enthalpy, Δ𝑆𝑑 is the
dissolution entropy, R is the gas constant (Angulo-Brown and Arias-Hernández, 1996).

Δ Hd Δ Sd
ln x= +
RT R

Recrystallization produces a solution by dissolving a solute in a solvent at or near its boiling point. When
a solute is exposed to a high temperature, its solubility in the solvent increases dramatically. When the
temperature is lowered, the solute dissolved in the solvent precipitates. Crash cooling crystallization is a
rapid cooling process that takes place in an ice water bath, whereas natural cooling crystallization is a
slow chilling process that takes place at room temperature and produces a modest number of liquid-filled
crystals. In this experiment we are going to use the Van't Hoff Equation to calculate the dissolving

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enthalpy and entropy of Epsom salt (MgSO4) in ethanol, acetone, and water. The crystal structure of
Epsom salt (MgSO4), sugar, and copper sulphate in water was also investigated in this experiment. This
experiment also will investigate the recrystallization of Epsom salt through crash and natural cooling
crystallisation.

2. Methodology
2.1. Materials

Epsom salt (MgSO4) (Sigma Aldrich, Reagent Plus®, ≥99.0%), copper sulphate (Sigma Aldrich, ACS
reagent, ≥98%), sugar, ethanol (Merck, standard for GC, ≥99.9%), acetone (Sigma Aldrich, ACS
reagent, ≥99.5%) and water.

2.2 Experimental

2.2.1 Dissolution enthalpy and entropy of Epsom salt

Firstly, nine of the empty crucibles are cleaned. Next, the crucibles are weighted by placing them on the
weight machine and the reading is recorded. Then, 10mL of solvents which are acetone, ethanol, and
water will be measured using a measuring cylinder and the solvents are poured into a small breaker with
different labels. The solvents are then heated until 30 ℃ by the hot plate and Epsom salt is added into the
solvents to make the solution become a saturated solution. Then, the solvents are stirred constantly until
the solution is well mixed. The temperature of the solutions is maintained at 30 ℃. The solutions are then
filtered into crucible using filter paper. The solution in the crucible is weighted using weighing machine to
measure the wet weight. Lastly, the crucible with the solutions is transferred into furnaces and will be left
overnight to let the solutions dry to obtain the dry weight. Step 3 to step 7 is repeated for 40 ℃ and 50 ℃.
The data are recorded in the table form.

2.2.2 Different types of crystal

Firstly, the initial weight of three empty crucibles is weighted using weighing machine. 10 mL of water at
50℃ is used as the solvent and followed by adding sugar into the water for dissolution. For crystallization
process, the solution is placed in the furnace. The crucible is taken out after 24 hours and weighted. Step 2
and 3 is repeated by replacing the sugar with copper sulphate and Epsom salt. Lastly, the solubility of the
sugar, copper sulphate, and Epsom salt in water and the weight of the crystals are recorded.

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3. Result and discussion

3.1. Part A: Solubility, Dissolution Enthalpy, ΔH and Dissolution Entropy, ΔS of Epsom Salt
(MgSO 4 )

Volume of solvent = 10 ml

Table 3.1: Experimental Results of Epsom Salt at Different Temperature in Ethanol, Acetone
and Water

Empty
Temperature Crucible Wet Dry Solubility
Solvent (°C) Weight (g) Weight (g) Weight (g) (g/ml)
30 28.2460 35.2807 32.8286 0.4583
Ethanol 40 28.4280 36.3440 33.4044 0.4976
50 29.1252 37.2550 34.6172 0.5492
30 28.6230 29.1671 28.8471 0.0224
Acetone 40 28.5731 29.4692 28.9581 0.0385
50 29.3100 30.5241 29.8703 0.0560
30 29.2230 43.7553 38.8940 0.9671
Water 40 28.1580 44.1944 39.0920 1.0934
50 29.6134 48.0093 41.6564 1.2043

Based on the results, the solubility of the salt was calculated by using the equation:

Dry weight ( g )−Empty crucible weight(g)

Solublity=
10 ml

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Solubility vs Temperature
1.4000

1.2000

1.0000
Solubility (g/ml)

0.8000 Ethanol
Acetone
0.6000 Water

0.4000

0.2000

0.0000
25 30 35 40 45 50 55
Temperature (°C)

Fig 3.1: Graph of Solubility of Epson Salt vs Temperature in Ethanol, Acetone and Water

In Figure 3.1, it shows that the solubility of Epsom salt in ethanol, acetone and water were
increased proportionally with temperature. This is because when the temperature was increased,
the kinetic energy will also be increased. The increase in kinetic energy allows solvent molecules
to overcome the attractive force among solute particles.[1] Besides, water had the highest
solubility then followed by ethanol and acetone. The solubility depends on the nature of the
solute and solvent. The substances with similar polarity will tend to mix with each other more
easily.[2] Epsom salt is an ionic compound with a positive magnesium ion ( Mg 2+¿¿) and a
negative sulphate ion ( SO2−¿4
¿
) which can be interacted to dissolve in a polar solvent. Water is
polar because of its bent shape which consists of hydroxyl group (-OH) to attract each other polar
molecules. The ethyl group (-CH2CH3) in ethanol is non-polar while the hydroxyl group (-OH) in
ethanol is polar. It is less polar than water. Acetone consists of non-polar methyl groups (-CH 3)
and polar carbonyl group (C=O). It is less polar than ethanol. The polarity of water is higher than
ethanol while the polarity of ethanol is higher than acetone. Hence, the Epsom salt is more
soluble in water and less soluble in acetone.

The Van’t Hoff equation reflects the relationship between the mole fraction solubility of a solute
and the temperature in a real solution, which is expressed as follows:

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−∆ H d ∆ Sd
ln x 1= +
RT R

where x 1 = equilibrium constant, K eq , ∆ H d = dissolution enthalpy (J/mol), ∆ S d= dissolution

entropy (J/mol.K), T = temperature (K) and R = gas constant (8.314 J/mol.K).

In order to calculate ∆ H d and ∆ S d, the equation can be expressed as below:

y=mx+c

−∆ H d 1 ∆ Sd
where y = ln K eq , m = ,x= ,c= .
R T R

The equilibrium constant, K eq was calculated by using the equation:

Weight of Epsom Salt

MW of Epsom Salt
K eq =
Weight of EpsomSalt Weight of Solvent
+
MW of Epsom Salt MW of Slovent

where Weight of Epson Salt = Dry Weight – Empty Crucible Weight

Weight of Solvent = Wet Weight – Dry Weight

According to PubChem, the molecular weight of Epsom salt, ethanol, acetone and water are
120.37 g/mol, 46.07 g/mol, 58.08 g/mol and 18.015 g/mol respectively.[3][4][5][6]

Table 3.2: Data for Different solvents and Temperature Used in Van’t Hoff Equation

Temperature Equilibrium 1/T

Solvent (K) Constant, K eq ( K −1 ) ln K eq
303.15 0.4170 0.0033 -0.8747
Ethanol 313.15 0.3932 0.0032 -0.9335
323.15 0.4435 0.0031 -0.8131
303.15 0.2526 0.0033 -1.3761
Acetone 313.15 0.2666 0.0032 -1.3221
323.15 0.2925 0.0031 -1.2292
303.15 0.2294 0.0033 -1.4722
Water 313.15 0.2428 0.0032 -1.4154
323.15 0.2210 0.0031 -1.5095

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ln Keq vs 1/T
0.0000
0.0030 0.0032 0.0034
-0.2000
-0.4000
-0.6000
ln Keq

-0.8000
-1.0000 f(x) = − 292.04806788269 x + 0.059494209676408

-1.2000
-1.4000 f(x) = − 717.424209490201 x + 0.98343827381984

-1.6000 f(x) = 175.195836786455 x − 2.02553907773973

1/T

Ethanol Linear (Ethanol) Acetone

Linear (Acetone) Water Linear (Water)

Fig 3.2: Graph of ln K eq vs 1/T

In Figure 3.2, the Van’t Hoff plot for ethanol and acetone shows a negative slope
which indicating the reaction is endothermic process while for water shows a positive slope
indicating the reaction is exothermic process. The slope and y-intercept can be obtained by the
linear equation showing on the graph. The data obtained was used to calculate the dissolution
enthalpy and entropy.

The values of slope and y-intercept were multiplied with gas constant value R=3.142
J/mol.K in order to obtain the values of dissolution enthalpy and entropy.

Table 3.3: Data of Dissolution Enthalpy and Entropy for Ethanol, Acetone and Water

Solvent Slope Y-intercept Dissolution Dissolution

Enthalpy, ∆ H d Entropy, ∆ S d

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(J/mol) (J/mol.K)

Ethanol -292.05 0.0595 2428.1037 0.4947

Acetone -717.42 0.9834 5964.6299 8.1760

Water 175.2 -2.0255 1456.6128 -16.8400

According to Table 3.3, ethanol, acetone and water have positive dissolution
enthalpy. The positive dissolution enthalpy shows that it is an endothermic process which absorbs
heat to the system. Besides, ethanol and acetone have positive dissolution entropy while water
has negative dissolution entropy. Positive dissolution entropy indicates a growth in disorder as all
spontaneous changes occur as the entropy of the universe increase.

3.2. Part B: Different Type of Crystal

Solvent: Water

Temperature: 50℃

Volume: 10 ml

Table 3.4: Weight of Solid Before and After the Crystallization Process

Component Empty Wet Weight (g) Dry Weight (g) Solubility

Crucible (g/ml)
Weight (g)

Sugar 28.1409 49.5288 41.5120 1.3371

Copper Sulfate 29.5130 46.4530 37.3600 0.7847

Epsom Salt 28.5503 48.0050 39.1250 1.0575

Table 3.5: The observation of Solid Appearance Before and After the Crystallization

Component Solid Appearance

Before After

Sugar Clear Crystallize

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Copper Sulfate Blue Colour Crystallize

Epsom Salt Clear Crystallize

A good solvent for crystallization should have high solubility for the solute as well as
high potential recovery. Crystallization is based on the principles of solubility, a solute tend to be
more soluble in hot solvents than in cold solvents. When a saturated hot solution is allowed to
cool, the solute is no longer soluble in the solvent and forms crystals of pure compound. From
table 3.5, sugar, copper sulfate and Epsom salt are crystallized after 24 hours. The crystals
formed has their own shape. Both sugar and Epsom salt crystals formed are in monoclinic prisms
shape [7] while copper sulfate crystal formed is in triclinic shape [8].

3.3. Part C: Crash Cooling vs Natural Cooling Crystallization

Solvent: Water

Temperature: 55℃

Volume: 50 ml

Table 3.6: Crash Cooling vs Natural Cooling Crystallization

Ice Bath Cooling Natural Cooling

Time Temperature Observation Temperature Observation

2 51 No Crystal 54 No Crystal

4 45 No Crystal 52 No Crystal

6 36 No Crystal 49 No Crystal

8 29 No Crystal 45 No Crystal

10 25 No Crystal 42 No Crystal

12 19 No Crystal 40 No Crystal

14 16 No Crystal 38 No Crystal

15 13 No Crystal 36 No Crystal

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16 9 No Crystal 35 No Crystal

20 6 Crystalize 35 No Crystal

21 5 Crystalize 35 No Crystal

Table 3.6 has showed the differences between the ice bath cooling and natural
cooling crystallization in different range of time and temperature. For the ice bath cooling, the
temperature decreased from 51℃ to 5℃ over 21 minutes. There is no crystal formed before 20
minutes, however the crystallization occurred after 20 minutes. For natural cooling, the
temperature decreased from 54℃ to 35℃ over 21 minutes. There is no crystal formed over the
whole time. This is because the ice bath increased the rate of crystallization when the temperature
decreased more rapidly. The solute and solvent passed through a homogeneous phase and form a
solid particle for both ice bath cooling and natural cooling.

4.0 Conclusion and recommendations

In conclusion, as the temperature rose, the solute's solubility in the solvent rose as well,
owing to the solvent molecules gaining more kinetic energy to break apart the solutes kept
together by intermolecular attractions. The highest dissolution enthalpy of acetone was
21346.195 J/mol, indicated that the reaction absorbs a lot of heat, followed by ethanol
(17850.158 J/mol) and water (10471.483 J/mol). Epsom salt had a higher solubility in water than
other salts because water and salt were more compatible in forming ionic compounds. Epsom
salt, for example, was less soluble in acetone due to its lower polarity than water and ethanol. At
50⁰C, water solvent had the highest solubility (1.204 g/mL), followed by ethanol (0.900g/mL)
and acetone (0.054g/mL). Besides, acetone absorbed the highest enthalpy heat for the reaction
which were 21346.195 (J/mol). Ethanol had the highest dissolution entropy 46.5526 (J/mol.k). It
was found out that different solute will result in different appearances and structure of crystal
after heating. Furthermore, the Van't Hoff plot found a negative slope, indicating that this
experiment was an endothermic reaction in all solvents. Moreover, the crystal structure of sugar,
copper sulphate, and Epsom salt in distilled water was observed to be monoclinic, triclinic, and
orthorhombic, respectively, based on the observation. According to the results of Epsom salt
recrystallization using ice batch cooling and natural cooling crystallization, a large amount of
crystal was formed from the 15th onwards during ice bath cooling as the cold condition promoted
crystal formation, whereas no crystal was formed during natural cooling.

As recommendation, Epsom salt should be added slowly to the solvent and the solution
must be stirred thoroughly until the solute was excess in solvent in order to ensure the accuracy

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of solubility. Moreover, Epsom salt in the solvent must be stirred at required speed to avoid mass
transfer resistance to be occurred between the solute and solvent as an assurance of accuracy in
determining solubility. Last but not least, equipment such as Scanning Electron Microscopy
(SEM) should be used in study the structure of crystal form instead of only calculating the
solubility of each type of crystal.

References

[1] Lumen. (n.d). Factors Affecting Solubility. Retrieved from https://courses.lumenlearning.com/boundless-

chemistry/chapter/factors-affecting-solubility/#:~:text=For%20many%20solids%20dissolved%20in,held%20together
%20by%20intermolecular%20attractions.

[2] Byju’s. (2022). Factors Affecting Solubility. Retrieved from https://byjus.com/chemistry/factors-affecting-

solubility/

[3] PubChem. (n.d.). COMPOUND SUMMARY Ethanol. Retrieved from

https://pubchem.ncbi.nlm.nih.gov/compound/Ethanol

[4] PubChem. (n.d.). COMPOUND SUMMARY Acetone. Retrieved from

https://pubchem.ncbi.nlm.nih.gov/compound/Acetone

[5] PubChem. (n.d.). COMPOUND SUMMARY Water. Retrieved from

https://pubchem.ncbi.nlm.nih.gov/compound/Water

[6] PubChem. (n.d.). COMPOUND SUMMARY Magnesium Sulfate. Retrieved from

https://pubchem.ncbi.nlm.nih.gov/compound/Magnesium-sulfate

[7] ingridscience.ca. (n.d.). Crystal shape observation with magnifiers/microscope. Retrieved

from https://www.ingridscience.ca/node/155

[8] Robolab Technologies. (2021). Purification of Copper Sulphate by Crystallization.

Retrieved from https://www.robolab.in/purification-of-copper-sulphate-by-crystallization/

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Appendix

Raw Data Provided

Part A

Calculation for Solubility of Epsom Salt

Dry weight ( g )−Empty crucible weight( g)

Solublity=
10 ml

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Solvent: Ethanol Solvent: Ethanol Solvent: Ethanol

Temperature: 30℃ Temperature: 40℃ Temperature: 50℃

Volume = 10ml Volume = 10ml Volume = 10ml

Solublity Solublity Solublity

32.8286−28.2460 33.4044−28.4280 34.6172−29.1252

¿ ¿ ¿
10 ml 10 ml 10 ml

¿ 0.4583 g/ml ¿ 0.4976 g/ml ¿ 0.5492 g/ml

 Same calculation for Acetone and Water at different temperature.

Calculation for Equilibrium constant ( K eq )

Weight of Epsom Salt

MW of Epsom Salt
K eq =
Weight of EpsomSalt Weight of Solvent
+
MW of Epsom Salt MW of Slovent

Weight of Epsom Salt = Dry Weight – Empty Crucible

Weight of Solvent = Wet Weight – Dry Weight

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Molecular Weight (MW) of Compound:

Epsom Salt = 120.37 g/mol

Ethanol = 46.07 g/mol

Acetone = 58.08 g/mol

Water = 18.015 g/mol

Solvent: Ethanol Solvent: Ethanol Solvent: Ethanol

Temperature: 30℃ Temperature: 40℃ Temperature: 50℃

Weight of Epsom Salt Weight of Epsom Salt Weight of Epsom Salt

= 32.8286 – 28.2460 = 33.4044 – 28.4280 = 34.6172 – 29.1252

= 4.5826 = 4.9764 = 5.4920

Weight of Solvent Weight of Solvent Weight of Solvent

= 35.2807 – 32.8286 = 36.3440 – 33.4044 = 37.2550 – 34.6172

= 2.4521 = 2.9396 = 2.6378

4.5826 4.9764 5.4920

120.37 120.37 120.37
K eq = K eq = K eq =
4.5826 2.4521 4.9764 2.9396 5.4920 2.6378
+ + +
120.37 46.07 120.37 46.07 120.37 46.07

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¿ 0.4170 ¿ 0.3932 ¿ 0.4435

 Same calculation for Acetone and Water at different temperature.

Calculation for Dissolution Enthalpy of Solvent used

∆ Hd
Slope, m ¿−
R

Dissolution enthalpy, ∆ H d = - mR

Gas constant, R = 8.314 g/mol.K

Solvent: Ethanol Solvent: Ethanol Solvent: Ethanol

Temperature: 30℃ Temperature: 40℃ Temperature: 50℃

Dissolution enthalpy Dissolution enthalpy Dissolution enthalpy

= - (-292.05 x 8.314) = - (-717.42 x 8.314) = - (175.2 x 8.314)

= 2428.1037 J/mol = 5964.6299 J/mol = 1456.6128 J/mol

 Same calculation for Acetone and Water at different temperature.

Calculation for Dissolution Entropy of Solvent used

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∆ Sd
Y-intercept, c ¿−
R

Dissolution enthalpy, ∆ S d = cR

Gas constant, R = 8.314 g/mol.K

Solvent: Ethanol Solvent: Ethanol Solvent: Ethanol

Temperature: 30℃ Temperature: 40℃ Temperature: 50℃

Dissolution enthalpy Dissolution enthalpy Dissolution enthalpy

= 0.0595 x 8.314 = 0.9834 x 8.314 = -2.0255 x 8.314

= 0.4947 J/mol.K = 8.1760 J/mol.K = -16.8400 J/mol.K

Part B

Calculation for Solubility of Component Used

Dry weight ( g )−Empty crucible weight( g)

Solublity=
10 ml

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Solvent: Water Solvent: Water Solvent: Water

Component = Sugar Component = Copper Sulfate Component = Epsom Salt

Temperature: 50℃ Temperature: 50℃ Temperature: 50℃

Volume = 10ml Volume = 10ml Volume = 10ml

Solublity Solublity Solublity

41.5120−28.1409 37.3600−29.5130 39.1250−28.5503

¿ ¿ ¿
10 ml 10 ml 10 ml

¿ 1.3371 g/ml ¿ 0.7847 g/ml ¿ 1.0575 g/ml

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