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Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen?

Published on May 20, 2016

1/8/2017 Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? | Nikhilesh Mukherjee |Home Profile  Search for people, jobs, companies, and more...  Advanced  My Network Learning Jobs Interests Business Services   4 Try Premium for free Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? Published on May 20, 2016 Nikhilesh Mukherjee Author and Consultant 7 1 0 Abstract The retrograde or inverse solubility, exists when a salt's dissolution is exothermic; according to Le Chatelier's principle, extra heat will cause the equilibrium for an exothermic process to shift towards the reactants. Sodium chloride and ammonium nitrate absorb heat while dissolving in water. They show direct solubility in water with temperature. Calcium phosphate and calcium sulfate are two typical salts which show retrograde solubility. Both Calcium phosphate and calcium sulfate evolve heat when they are dissolved. Let us start with basics. What is solubility? Solubility is an ability of a substance to dissolve. The substance which is being dissolved is called a solute and the substance in which the solute is dissolved is called a solvent. A mixture of solute and solvent is called a solution. It is measured in terms of the maximum amount of solute dissolved in a solvent at equilibrium at a given temperature and pressure. When there is no more dissolution of solute in the solvent the https://www.linkedin.com/pulse/mystery­solubility­retrograde­temperature­inverse­why­mukherjee 1/6 " id="pdf-obj-0-20" src="pdf-obj-0-20.jpg">

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1/8/2017 Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? | Nikhilesh Mukherjee |Home Profile  Search for people, jobs, companies, and more...  Advanced  My Network Learning Jobs Interests Business Services   4 Try Premium for free Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? Published on May 20, 2016 Nikhilesh Mukherjee Author and Consultant 7 1 0 Abstract The retrograde or inverse solubility, exists when a salt's dissolution is exothermic; according to Le Chatelier's principle, extra heat will cause the equilibrium for an exothermic process to shift towards the reactants. Sodium chloride and ammonium nitrate absorb heat while dissolving in water. They show direct solubility in water with temperature. Calcium phosphate and calcium sulfate are two typical salts which show retrograde solubility. Both Calcium phosphate and calcium sulfate evolve heat when they are dissolved. Let us start with basics. What is solubility? Solubility is an ability of a substance to dissolve. The substance which is being dissolved is called a solute and the substance in which the solute is dissolved is called a solvent. A mixture of solute and solvent is called a solution. It is measured in terms of the maximum amount of solute dissolved in a solvent at equilibrium at a given temperature and pressure. When there is no more dissolution of solute in the solvent the https://www.linkedin.com/pulse/mystery­solubility­retrograde­temperature­inverse­why­mukherjee 1/6 " id="pdf-obj-0-26" src="pdf-obj-0-26.jpg">

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1/8/2017 Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? | Nikhilesh Mukherjee |Home Profile  Search for people, jobs, companies, and more...  Advanced  My Network Learning Jobs Interests Business Services   4 Try Premium for free Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? Published on May 20, 2016 Nikhilesh Mukherjee Author and Consultant 7 1 0 Abstract The retrograde or inverse solubility, exists when a salt's dissolution is exothermic; according to Le Chatelier's principle, extra heat will cause the equilibrium for an exothermic process to shift towards the reactants. Sodium chloride and ammonium nitrate absorb heat while dissolving in water. They show direct solubility in water with temperature. Calcium phosphate and calcium sulfate are two typical salts which show retrograde solubility. Both Calcium phosphate and calcium sulfate evolve heat when they are dissolved. Let us start with basics. What is solubility? Solubility is an ability of a substance to dissolve. The substance which is being dissolved is called a solute and the substance in which the solute is dissolved is called a solvent. A mixture of solute and solvent is called a solution. It is measured in terms of the maximum amount of solute dissolved in a solvent at equilibrium at a given temperature and pressure. When there is no more dissolution of solute in the solvent the https://www.linkedin.com/pulse/mystery­solubility­retrograde­temperature­inverse­why­mukherjee 1/6 " id="pdf-obj-0-30" src="pdf-obj-0-30.jpg">

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1/8/2017 Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? | Nikhilesh Mukherjee |Home Profile  Search for people, jobs, companies, and more...  Advanced  My Network Learning Jobs Interests Business Services   4 Try Premium for free Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? Published on May 20, 2016 Nikhilesh Mukherjee Author and Consultant 7 1 0 Abstract The retrograde or inverse solubility, exists when a salt's dissolution is exothermic; according to Le Chatelier's principle, extra heat will cause the equilibrium for an exothermic process to shift towards the reactants. Sodium chloride and ammonium nitrate absorb heat while dissolving in water. They show direct solubility in water with temperature. Calcium phosphate and calcium sulfate are two typical salts which show retrograde solubility. Both Calcium phosphate and calcium sulfate evolve heat when they are dissolved. Let us start with basics. What is solubility? Solubility is an ability of a substance to dissolve. The substance which is being dissolved is called a solute and the substance in which the solute is dissolved is called a solvent. A mixture of solute and solvent is called a solution. It is measured in terms of the maximum amount of solute dissolved in a solvent at equilibrium at a given temperature and pressure. When there is no more dissolution of solute in the solvent the https://www.linkedin.com/pulse/mystery­solubility­retrograde­temperature­inverse­why­mukherjee 1/6 " id="pdf-obj-0-34" src="pdf-obj-0-34.jpg">

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Abstract

The retrograde or inverse solubility, exists when a salt's dissolution is exothermic; according to Le Chatelier's principle, extra heat will cause the equilibrium for an exothermic process to shift towards the reactants. Sodium chloride and ammonium nitrate absorb heat while dissolving in water. They show direct solubility in water with temperature. Calcium phosphate and calcium sulfate are two typical salts which show retrograde solubility. Both Calcium phosphate and calcium sulfate evolve heat when they are dissolved.

Let us start with basics.

What is solubility?

Solubility is an ability of a substance to dissolve. The substance which is being dissolved is called a solute and the substance in which the solute is dissolved is called a solvent. A mixture of solute and solvent is called a solution. It is measured in terms of the maximum amount of solute dissolved in a solvent at equilibrium at a given temperature and pressure. When there is no more dissolution of solute in the solvent the

1/8/2017

Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? | Nikhilesh Mukherjee | Pulse | LinkedIn

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solution is called a saturated solution. Solubility is expressed usually as grams of solute

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per 100 grams of solvent.

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What makes things dissolve?

In the process of dissolving, molecules of the solute are inserted into a solvent and surrounded by its molecules. In order for this process to take place, intermolecular bonds between molecules of solute and molecules of solvent have to be broken and new molecular bonds between solute and solvent have to be formed.

Role of temperature?

Generally, the solubility of a given solute in a given solvent typically depends on temperature. Many salts show a large increase in solubility with temperature. This can be explained like this. As the temperature of a solution is increased, the average kinetic energy of the molecules that make up the solution also increases. This increase in kinetic energy allows the solvent molecules to more effectively break apart the solute molecules that are held together by intermolecular attractions. The average kinetic energy of the solute molecules also increases with temperature, and it destabilizes the solid state. The increased vibration (kinetic energy) of the solute molecules causes them to be less able to hold together, and thus they dissolve more readily.

There are, however, exceptions. Some solutes exhibit solubility that is fairly independent of temperature. There some solutes which become less soluble with increase in temperature.

What is retrograde solubility?

A few, solutes like calcium carbonate, calcium phosphate, calcium sulfate magnesium silicate etc., become less soluble in water as temperature increases. This inverse temperature dependence is sometimes referred to as retrograde or inverse solubility,

1/8/2017

Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? | Nikhilesh Mukherjee | Pulse | LinkedIn

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Implications of retrograde solubility

One of the most important implications of retrograde solubility is the deposit of scale forming salts like calcium carbonate, calcium phosphate, calcium sulfate, magnesium silicate etc., on heat transfer surfaces when they precipitate after their solubility have exceeded either in the bulk water or at the surface because of increased temperature. The salts with the "normal" solubility increase their solubility with increasing temperature and thus will foul the cooling surfaces. The salts with "inverse" or "retrograde" solubility will foul the heating surfaces.

Why does some salts show retrograde solubility?

This can be best explained by the Le Chatelier principle

What is Le Chatelier principle?

It states that if a dynamic equilibrium is disturbed by changing the conditions, the position of equilibrium moves to counteract the change.

What does it mean?

Let us take a reaction, A + 2B < ­­­­­­ > C + D , Delta H = ­ 250 kj/mol . Assume that forward reaction is exothermic, 250 kj/mol heat is evolved when 1 mole of A reacts completely with 2 moles of B. The reverse reaction , the conversion of C and D into A and B, would be endothermic by exactly the same amount.

Let us now examine what happens if we change the conditions by increasing the temperature?

1/8/2017

Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? | Nikhilesh Mukherjee | Pulse | LinkedIn

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Suppose the system is in equilibrium at 300°C, and we increase the temperature to

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500°C. How can the reaction counteract the change we have made according to Le

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Chatelier principle? How can it cool itself down again? To cool down, it needs to absorb the extra heat that we have just put in. In other words , the position of equilibrium,

therefore, has to move to the left, in the direction when the reaction is endothermic. The new equilibrium mixture contains more A and B, and less C and D.

Let us take the second case.

What would happen if we change the conditions by decreasing the temperature?

The equilibrium will move in such a way that the temperature increases again. Let us see how it happens. Suppose the system is in equilibrium at 500°C and we reduce the temperature to 400°C. The reaction will tend to heat itself up again to return to the original temperature. It can only do that by favoring the exothermic reaction. That is the position of equilibrium will move to the right. More A and B are converted into C and D at the lower temperature.

A + 2B < ­­­­­­ > C + D , Delta H = ­ 250 kj/mol

Summary

  • Increasing the temperature of a system in dynamic equilibrium favors the endothermic reaction. The system counteracts the change you have made by absorbing the extra heat.

  • Decreasing the temperature of a system in dynamic equilibrium favors the exothermic reaction. The system counteracts the change you have made by producing more heat.

Let us apply this concept to solubility.

Explanation for retrograde solubility

In any solution process where solute and solvent [water] are in dynamic equilibrium with the solution and heat is applied to the solution , the dynamic equilibrium will be disturbed. As per Le Chatelier principle, the disturbed equilibrium will be opposed by a shift in the position of equilibrium. If the solution process is exothermic that is if the solution of solute in water generates heat , the position of the equilibrium will shift to left, that is, in a direction when the process is endothermic to counter the disturbed equilibrium. As a consequence to this, the dissolution process will be slowed down . There will be more undissolved solute in water. The solute will show a retrograde solubility in water with respect to temperature.

Exactly in the same manner, if the solute absorbs heat while going into solution in water, in order to counter the change in the thermodynamic equilibrium , you have to

1/8/2017

Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? | Nikhilesh Mukherjee | Pulse | LinkedIn

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supply more heat to dissolve more solute in the solvent by shifting the position of the

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equilibrium to right. In other words the dissolution process will depend on the supply of

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heat and proportionately increase with temperature. The solute will show direct or prograde solubility with respect water.

Let us take some examples.

Both sodium chloride and ammonium nitrate absorb heat while dissolving in water. They show direct solubility in water with temperature. Calcium phosphate and calcium sulfate are two typical salts which show retrograde solubility. Both Calcium phosphate and calcium sulfate evolve heat when they are dissolved.

It can be concluded that if dissolution of a solute in a solvent would show a retrograde solubility or a direct solubility with temperature depends on the heat of solution. While dissolving, when a solute evolves heat, the solute shows a retrograde solubility with temperature. When a solute absorbs heat while dissolving, it has a direct relation with temperature.

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1/8/2017 Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? | Nikhilesh Mukherjee |Home Home Home Home Home Profile Profile Profile Profile Profile      supply more heat to dissolve more solute in the solvent by shiftin g the p osition of th e      Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Advanced Advanced Advanced Advanced Advanced   4   4   4   4   4 equilibriu m to ri ght. In o ther words the dissolution process will depend on the suppl y of Learning Learning Learning Learning Learning Jobs Jobs Jobs Jobs Jobs Interests Interests Interests Interests Interests Business Services Business Services Business Services Business Services My Network My Network My Network My Network My Network Business Services Try Premium for free Try Premium for free Try Premium for free Try Premium for free Try Premium for free heat and proportionately increase with temperature. The solute will show direct or prograde solubility with respect water. Let us take some examples. Both sodium chloride and ammonium nitrate absorb heat while dissolving in water. They show direct solubility in water with temperature. Calcium phosphate and calcium sulfate are two typical salts which show retrograde solubility. Both Calcium phosphate and calcium sulfate evolve heat when they are dissolved. It can be concluded that if dissolution of a solute in a solvent would show a retrograde solubility or a direct solubility with temperature depends on the heat of solution. While dissolving, when a solute evolves heat, the solute shows a retrograde solubility with temperature. When a solute absorbs heat while dissolving, it has a direct relation with temperature. Tagged in: solubility , chemistry Report this Nikhilesh Mukherjee Author and Consultant 57 articles 1 comment Leave your thoughts here… Prof. Aiman Eid Al-Rawajfeh Full Professor at Tafila Technical University Very interesting, thank you. Like Reply Recommended 8mo Don't miss more articles by Nikhilesh Mukherjee What changes Enthalpy of a Chemical reaction: Kinetic energy or Potential energy or something else? Metallurgy: What is metallic bond? How it explains unique features of metals? Nikhilesh Mukherjee on LinkedIn What decides whether a chemical reaction would happen - Thermodynamics or Kinetics? https://www.linkedin.com/pulse/mystery­solubility­retrograde­temperature­inverse­why­mukherjee 5/6 " id="pdf-obj-4-147" src="pdf-obj-4-147.jpg">

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1/8/2017 Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? | Nikhilesh Mukherjee |Home Home Home Home Home Profile Profile Profile Profile Profile      supply more heat to dissolve more solute in the solvent by shiftin g the p osition of th e      Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Advanced Advanced Advanced Advanced Advanced   4   4   4   4   4 equilibriu m to ri ght. In o ther words the dissolution process will depend on the suppl y of Learning Learning Learning Learning Learning Jobs Jobs Jobs Jobs Jobs Interests Interests Interests Interests Interests Business Services Business Services Business Services Business Services My Network My Network My Network My Network My Network Business Services Try Premium for free Try Premium for free Try Premium for free Try Premium for free Try Premium for free heat and proportionately increase with temperature. The solute will show direct or prograde solubility with respect water. Let us take some examples. Both sodium chloride and ammonium nitrate absorb heat while dissolving in water. They show direct solubility in water with temperature. Calcium phosphate and calcium sulfate are two typical salts which show retrograde solubility. Both Calcium phosphate and calcium sulfate evolve heat when they are dissolved. It can be concluded that if dissolution of a solute in a solvent would show a retrograde solubility or a direct solubility with temperature depends on the heat of solution. While dissolving, when a solute evolves heat, the solute shows a retrograde solubility with temperature. When a solute absorbs heat while dissolving, it has a direct relation with temperature. Tagged in: solubility , chemistry Report this Nikhilesh Mukherjee Author and Consultant 57 articles 1 comment Leave your thoughts here… Prof. Aiman Eid Al-Rawajfeh Full Professor at Tafila Technical University Very interesting, thank you. Like Reply Recommended 8mo Don't miss more articles by Nikhilesh Mukherjee What changes Enthalpy of a Chemical reaction: Kinetic energy or Potential energy or something else? Metallurgy: What is metallic bond? How it explains unique features of metals? Nikhilesh Mukherjee on LinkedIn What decides whether a chemical reaction would happen - Thermodynamics or Kinetics? https://www.linkedin.com/pulse/mystery­solubility­retrograde­temperature­inverse­why­mukherjee 5/6 " id="pdf-obj-4-193" src="pdf-obj-4-193.jpg">

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1/8/2017 Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? | Nikhilesh Mukherjee |Nikhilesh M ukherjee on LinkedIn Home Home Home Home Home Home Profile Profile Profile Profile Profile Profile My Network My Network My Network My Network My Network My Network      Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Learning Learning Learning Learning Learning Learning Jobs Jobs Jobs Jobs Jobs Jobs Interests Interests Interests Interests Interests Interests       Nikhilesh Mukherjee on Link edIn Advanced Advanced Advanced Advanced Advanced Advanced Business Services Try Premium for free Business Services Try Premium for free Business Services Try Premium for free Business Services Business Services Business Services Try Premium for free Try Premium for free Try Premium for free Looking for more of the latest headlines on LinkedIn? Discover more stories Help Center About Careers Advertising LinkedIn Corporation © 2017 User Agreement Talent Solutions Sales Solutions Small Business Mobile Language Upgrade Your Account Privacy Policy Ad Choices Community Guidelines Cookie Policy Copyright Policy Send Feedback https://www.linkedin.com/pulse/mystery­solubility­retrograde­temperature­inverse­why­mukherjee 6/6 " id="pdf-obj-5-154" src="pdf-obj-5-154.jpg">
1/8/2017 Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? | Nikhilesh Mukherjee |Nikhilesh M ukherjee on LinkedIn Home Home Home Home Home Home Profile Profile Profile Profile Profile Profile My Network My Network My Network My Network My Network My Network      Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Learning Learning Learning Learning Learning Learning Jobs Jobs Jobs Jobs Jobs Jobs Interests Interests Interests Interests Interests Interests       Nikhilesh Mukherjee on Link edIn Advanced Advanced Advanced Advanced Advanced Advanced Business Services Try Premium for free Business Services Try Premium for free Business Services Try Premium for free Business Services Business Services Business Services Try Premium for free Try Premium for free Try Premium for free Looking for more of the latest headlines on LinkedIn? Discover more stories Help Center About Careers Advertising LinkedIn Corporation © 2017 User Agreement Talent Solutions Sales Solutions Small Business Mobile Language Upgrade Your Account Privacy Policy Ad Choices Community Guidelines Cookie Policy Copyright Policy Send Feedback https://www.linkedin.com/pulse/mystery­solubility­retrograde­temperature­inverse­why­mukherjee 6/6 " id="pdf-obj-5-156" src="pdf-obj-5-156.jpg">

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1/8/2017 Mystery of solubility: Retrograde [Temperature Inverse] solubility: Why does it happen? | Nikhilesh Mukherjee |Nikhilesh M ukherjee on LinkedIn Home Home Home Home Home Home Profile Profile Profile Profile Profile Profile My Network My Network My Network My Network My Network My Network      Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Search for people, jobs, companies, and more... Learning Learning Learning Learning Learning Learning Jobs Jobs Jobs Jobs Jobs Jobs Interests Interests Interests Interests Interests Interests       Nikhilesh Mukherjee on Link edIn Advanced Advanced Advanced Advanced Advanced Advanced Business Services Try Premium for free Business Services Try Premium for free Business Services Try Premium for free Business Services Business Services Business Services Try Premium for free Try Premium for free Try Premium for free Looking for more of the latest headlines on LinkedIn? Discover more stories Help Center About Careers Advertising LinkedIn Corporation © 2017 User Agreement Talent Solutions Sales Solutions Small Business Mobile Language Upgrade Your Account Privacy Policy Ad Choices Community Guidelines Cookie Policy Copyright Policy Send Feedback https://www.linkedin.com/pulse/mystery­solubility­retrograde­temperature­inverse­why­mukherjee 6/6 " id="pdf-obj-5-190" src="pdf-obj-5-190.jpg">

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