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This project has received funding from the European Union’s Horizon 2020
research and innovation programme under grant agreement No 869993.
Supersaturation
Solubility curves
• Solubility defines the concentration of
a solution in which it is saturated.
• Saturated solution is at equilibrium.
• Solubility usually varies with the
temperature. Most substances are
more soluble at higher temperatures,
but there are some exceptions, for
example HCl and NH3.
• Solubilities can be expressed in
solubility curves.
• The temperature is on the x-axis and
y-axis indicates the amount of
the solute dissolved in 100 grams of
solvent.
Solubility curves for several compounds.
(CK-12 Foundation,Christopher Auyeung)
Solubility of sugars and sugar alcohols in water
Levels of supersaturation
• When the solution contains more than
the maximum amount of the solute, it
is called a supersaturated solution.
• Supersaturated solution is not at
equilibrium.
• When the level of supersaturation
is lightly increased, the solution gets
metastable.
• If the cooling is proceeded, the solution
achieves the supersaturation limit
and becomes unstable.
Driving force
• Supersaturation is a driving force for
crystallization.
• Spontaneous nucleation may only
occur above the supersaturation limit.
• In industrial crystallization, nucleation
is usually initiated by crystal seeds at
the metastable zone. That is where
the crystal growth also appears.
• Crystallization may continue to the
saturation curve at the most.
Expressions of supersaturation
• There are several ways to express the level of supersaturation. The most
commonly used are:
Concentration driving force ∆𝑐 = 𝑐 − 𝑐∗
Supersaturation ratio S =
𝑐
𝑐∗
Relative supersaturation 𝜎 =
∆𝑐
𝑐∗
= 𝑆 − 1
It is essential to mention the temperature, because solubility is temperature
dependent.
c = solution
concentration
c* = concentration of the
saturated solution at the
given temperature
Example: Level of supersaturation
• Solubility of sucrose in water is 2040 g/kg of water at 20 °C. Let c = 2450 g/kg.
Concentration driving force ∆𝑐 = 𝑐 − 𝑐∗
= 2450
g
kg
− 2040
g
kg
= 410
g
kg
Supersaturation ratio S =
𝑐
𝑐∗
=
2450 g/kg
2040 g/kg
≈ 1.20
Relative supersaturation 𝜎 =
∆𝑐
𝑐∗
=
410 g/kg
2040 g/kg
≈ 0.20
Alternative calculation 𝜎 = 𝑆 − 1 = 1.20 − 1 = 0.20
Different units of concentration
• It is essential to take into consideration the units of concentration used.
They affect the obtained values as shown in the table below.
• Let’s use the same values asc in the previous example (sucrose in water at 20
°C, c* = 2040 g/kg and c = 2450 g/kg). Molar mass of sucrose M ≈ 342 g/mol.
Solution densities ρc* = 1330 kg/m3 and ρc = 1360 kg/m3.
Solution
composition
c c* Δc S σ
g/kg water 2450 2040 410 1.20 0.20
g/kg solution 710 671 39 1.06 0.06
g/l solution 966 893 73 1.08 0.08
mol/l solution 2.82 2.61 0.21 1.08 0.08
mole fraction 0.114 0.097 0.017 1.18 0.18
This project has received funding from the European Union’s Horizon 2020
research and innovation programme under grant agreement No 869993.
References
Mullin, J. W. 2001. Crystallization. Oxford: Elsevier Science & Technology. pp. 123-130.
Myerson, A. S. (ed.) 2002. Handbook of Industrial Crystallization. Elsevier Inc. pp. 14-18.
Videos:
• Solubility vs concentration: https://youtu.be/cHBlDVg9nR8
• Saturated, unsaturated, supersaturated: https://youtu.be/s6KcCgnMnhA
• Solubility curves: https://youtu.be/VKmyj1z8T8U

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Supersaturation in crystallization

  • 1. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 869993. Supersaturation
  • 2. Solubility curves • Solubility defines the concentration of a solution in which it is saturated. • Saturated solution is at equilibrium. • Solubility usually varies with the temperature. Most substances are more soluble at higher temperatures, but there are some exceptions, for example HCl and NH3. • Solubilities can be expressed in solubility curves. • The temperature is on the x-axis and y-axis indicates the amount of the solute dissolved in 100 grams of solvent. Solubility curves for several compounds. (CK-12 Foundation,Christopher Auyeung)
  • 3. Solubility of sugars and sugar alcohols in water
  • 4. Levels of supersaturation • When the solution contains more than the maximum amount of the solute, it is called a supersaturated solution. • Supersaturated solution is not at equilibrium. • When the level of supersaturation is lightly increased, the solution gets metastable. • If the cooling is proceeded, the solution achieves the supersaturation limit and becomes unstable.
  • 5. Driving force • Supersaturation is a driving force for crystallization. • Spontaneous nucleation may only occur above the supersaturation limit. • In industrial crystallization, nucleation is usually initiated by crystal seeds at the metastable zone. That is where the crystal growth also appears. • Crystallization may continue to the saturation curve at the most.
  • 6. Expressions of supersaturation • There are several ways to express the level of supersaturation. The most commonly used are: Concentration driving force ∆𝑐 = 𝑐 − 𝑐∗ Supersaturation ratio S = 𝑐 𝑐∗ Relative supersaturation 𝜎 = ∆𝑐 𝑐∗ = 𝑆 − 1 It is essential to mention the temperature, because solubility is temperature dependent. c = solution concentration c* = concentration of the saturated solution at the given temperature
  • 7. Example: Level of supersaturation • Solubility of sucrose in water is 2040 g/kg of water at 20 °C. Let c = 2450 g/kg. Concentration driving force ∆𝑐 = 𝑐 − 𝑐∗ = 2450 g kg − 2040 g kg = 410 g kg Supersaturation ratio S = 𝑐 𝑐∗ = 2450 g/kg 2040 g/kg ≈ 1.20 Relative supersaturation 𝜎 = ∆𝑐 𝑐∗ = 410 g/kg 2040 g/kg ≈ 0.20 Alternative calculation 𝜎 = 𝑆 − 1 = 1.20 − 1 = 0.20
  • 8. Different units of concentration • It is essential to take into consideration the units of concentration used. They affect the obtained values as shown in the table below. • Let’s use the same values asc in the previous example (sucrose in water at 20 °C, c* = 2040 g/kg and c = 2450 g/kg). Molar mass of sucrose M ≈ 342 g/mol. Solution densities ρc* = 1330 kg/m3 and ρc = 1360 kg/m3. Solution composition c c* Δc S σ g/kg water 2450 2040 410 1.20 0.20 g/kg solution 710 671 39 1.06 0.06 g/l solution 966 893 73 1.08 0.08 mol/l solution 2.82 2.61 0.21 1.08 0.08 mole fraction 0.114 0.097 0.017 1.18 0.18
  • 9. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 869993. References Mullin, J. W. 2001. Crystallization. Oxford: Elsevier Science & Technology. pp. 123-130. Myerson, A. S. (ed.) 2002. Handbook of Industrial Crystallization. Elsevier Inc. pp. 14-18. Videos: • Solubility vs concentration: https://youtu.be/cHBlDVg9nR8 • Saturated, unsaturated, supersaturated: https://youtu.be/s6KcCgnMnhA • Solubility curves: https://youtu.be/VKmyj1z8T8U