Lattice Enthalpy, Hydration Enthalpy And Enthalpy Of Solution

Lattice Enthalpy, Hydration Enthalpy And Enthalpy Of Solution

Edited By Shivani Poonia | Updated on Jul 02, 2025 05:59 PM IST

Lattice enthalpy is the change in energy that takes place when one mole of any ionic compound is formed from its gaseous ions under standard conditions, usually taken to be at 298 K and under a pressure of 1 bar. Because the formation of strong ionic lattice bonds occurs, it is always negative and exothermic. High lattice enthalpy means that the ionic compound is pretty stable because lots of energy will be released when a lattice forms. Thus, for example, when solid sodium chloride NaCl is formed from the gaseous ions of sodium, Na⁺, and chloride, Cl⁻, much energy is released because the ions are united by very strong electrostatic forces.

This Story also Contains
  1. Lattice Enthalpy
  2. Heat of Hydration
  3. Heat of Solution
  4. Solubility Of an Ionic Compound In Water
  5. Some Solved Examples
  6. Summary
Lattice Enthalpy, Hydration Enthalpy And Enthalpy Of Solution
Lattice Enthalpy, Hydration Enthalpy And Enthalpy Of Solution

Lattice Enthalpy

The lattice enthalpy of an ionic compound is the enthalpy change that occurs when one mole of an ionic compound is formed from its ions in a gaseous state.

$\mathrm{Na}^{+}(\mathrm{g})+\mathrm{Cl}^{-}(\mathrm{g}) \longrightarrow \mathrm{NaCl}(\mathrm{s}), \Delta \mathrm{H}=-788 \mathrm{kJmole}^{-1}$

Heat of Hydration

The enthalpy change during hydration of one mole of any gaseous ion is called heat of hydration.

$\begin{aligned} & \mathrm{Na}^{+}(\mathrm{g}) \longrightarrow \mathrm{Na}^{+}(\mathrm{aq}), \Delta \mathrm{H}=\Delta \mathrm{H}_{\mathrm{hyd}_{\mathrm{Na}^2}+} \\ & \mathrm{Cl}^{-}(\mathrm{g}) \longrightarrow \mathrm{Cl}^{-}(\mathrm{aq}), \Delta \mathrm{H}=\Delta \mathrm{H}_{\mathrm{hyd}_{\mathrm{Cl}^{-}}} \\ & \end{aligned}$

Heat of Solution

It is a change in enthalpy when one mole of a solid solute is dissolved more than the solvent.

$\mathrm{NaCl}(\mathrm{s}) \longrightarrow \mathrm{Na}^{+}(\mathrm{aq})+\mathrm{Cl}^{-}(\mathrm{aq}), \Delta \mathrm{H}=\Delta \mathrm{H}_{\mathrm{sol}_{\mathrm{NaCl}}}$

Solubility Of an Ionic Compound In Water

When an ionic compound dissolves in a solvent, the ions leave their ordered positions on the crystal lattice. These are now more free in solution. But solvation of these ions (hydration in case the solvent is water) also occurs at the same time. The enthalpy of solution of any ionic solid, in water is, therefore, determined by the selective values of the lattice enthalpy and enthalpy of hydration of ions. This will be more clear with the help of the diagram given below:

Thus, the enthalpy of solution, enthalpy of hydration, and the lattice energy can be related as

$\Delta_{\text {sol }} \mathrm{H}^0=\Delta_{\text {lattice }} \mathrm{H}^0+\Delta_{\text {hyd }} \mathrm{H}^0$

For most of the ionic compounds, $\Delta_{\text {sol }} \mathrm{H}^0$ is positive and the dissociation process is endothermic. Therefore the solubility of most salts in water increases with the rise of temperature. If the lattice enthalpy is very high, the dissolution of the compound may not take place at all.

Recommended topic video on (Lattice Enthalpy, Hydration Enthalpy And Enthalpy Of Solution)


Some Solved Examples

Example 1: A solution of 500ml of 0.2M KOH and 500ml of 0.2M HCl is mixed and stirred. The temperature rise is T1. The experiment is repeated using 250ml of each of the solutions, the temperature raised is T2. Which of the following is true?

1) $T_1=T_2$
2) $T_1=2 T_2$
3) $T_1=4 T_2$
4) $T_2=9 T_1$

Solution

Suppose heat evolved in 1st case is Q1 and that in the second case is Q2.

$\begin{aligned} & \text { Then } Q_2=\frac{1}{2} Q_1 \quad \text { But } Q_1=1000 T_1 \\ & \text { and } Q_2=500 T_2 \\ & \Rightarrow 500 T_2=\frac{1}{2} \times 1000 T_1 \\ & \text { i.e } T_2=T_1\end{aligned}$

Example 2: Which of the following is the most favorable condition for the solubility of an ionic compound in water?

1)high lattice enthalpy and high hydration enthalpy of its ions

2) low lattice enthalpy and high hydration enthalpy of its ions

3)low lattice enthalpy and low hydration enthalpy of its ions

4)high lattice enthalpy and low hydration enthalpy of its ions

Solution

The solubility or the heat of solution of an ionic compound is related to the lattice energy and the heat of hydration of the ions

The enthalpy of solution, enthalpy of hydration, and the lattice energy can be related as

$\Delta_{\text {sol }} \mathrm{H}^0=\Delta_{\text {lattice }} \mathrm{H}^0+\Delta_{\text {hyd }} \mathrm{H}^0$

High negative values are a favorable condition for the solubility of ionic compounds

Thus, for greater solubility, the lattice energy should be low and the hydration enthalpy should be high.


Example 3: Enthalpy of solution of NaOH (solid) in water is -41.6 kJ/mol. When NaOH is dissolved in water, the temperature of water

1) increases

2)decreases

3)does not change

4)fluctuates indefinitely

Solution

When NaOH dissolves in water, then heat is released. Some part of this heat released will be used up by water and its temperature will be increased.

Example 4: Lattice energy is inversely proportional to the sum of radii of:

1)Cation

2)Anion

3)Atoms

4) Both cation and anion

Solution

Lattice energy is directly related to the product of the ion charges and inversely related to the internuclear distance (which is the sum of radii of cation and anion).

Summary

Lattice enthalpy is defined as the energy obtained from the combination of gaseous ions to make a solid ionic compound. This gives rise, in an exothermic process, to the potential strength of the ionic bonds within the lattice. One example is the case in which the formation of sodium chloride (NaCl) from sodium (Na⁺) and chloride (Cl⁻) ions is very exothermic because the ions are held together by very strong electrostatic forces. The high lattice enthalpy reflects a stable and tightly bound ionic crystal. Hydration enthalpies quantify the energy released when gaseous ions dissolve in water and they turn to hydrated ions.For example, sodium (Na⁺) and chloride (Cl⁻) ions will release energy in the way of hydration upon dissolution in water, as the ions will interact strongly with the polar water molecules.

Frequently Asked Questions (FAQs)

1. How does the concept of hydration shells relate to hydration enthalpy?
Hydration shells are the layers of water molecules that surround and interact with dissolved ions. The formation of these shells is directly related to hydration enthalpy. Ions with stronger hydration shells (typically smaller, more highly charged ions) have more negative hydration enthalpies, releasing more energy during the hydration process.
2. How does the hydration enthalpy of cations compare to that of anions of similar size?
Generally, cations have more negative hydration enthalpies than anions of similar size. This is because the electron-rich oxygen atoms in water molecules can approach cations more closely than anions, resulting in stronger ion-dipole interactions and more energy release during hydration.
3. What is hydration enthalpy, and how does it relate to the dissolution process?
Hydration enthalpy is the energy released when gaseous ions interact with water molecules to form hydrated ions. It's crucial in the dissolution process because it provides the energy needed to overcome the lattice enthalpy and break apart the ionic solid. The more negative the hydration enthalpy, the more energy is released during hydration.
4. What is the relationship between hydration enthalpy and ion solvation?
Hydration enthalpy is a measure of the energy released during ion solvation in water. The more negative the hydration enthalpy, the more favorable the solvation process. Ions with more negative hydration enthalpies tend to be more easily solvated and often have a greater degree of hydration (larger hydration shells).
5. How does the concept of hydration enthalpy relate to the Hofmeister series?
The Hofmeister series ranks ions based on their ability to salt out or salt in proteins. This ranking correlates with hydration enthalpies. Ions with more negative hydration enthalpies (kosmotropes) tend to salt out proteins, while those with less negative hydration enthalpies (chaotropes) tend to salt in proteins.
6. What is the enthalpy of solution, and how is it related to lattice and hydration enthalpies?
The enthalpy of solution is the overall energy change when an ionic compound dissolves in water. It's the sum of the lattice enthalpy (endothermic) and the hydration enthalpy (exothermic). Mathematically, it can be expressed as: ΔHsolution = ΔHlattice + ΔHhydration
7. Can you explain why some dissolution processes are endothermic while others are exothermic?
The overall enthalpy change during dissolution depends on the relative magnitudes of lattice enthalpy and hydration enthalpy. If the energy released by hydration exceeds the energy required to break the lattice, the process is exothermic (releases heat). If more energy is needed to break the lattice than is released by hydration, the process is endothermic (absorbs heat).
8. Why do some salts, like CaCl2, produce heat when dissolved in water?
Salts like CaCl2 produce heat (exothermic dissolution) because the energy released during hydration of the ions (hydration enthalpy) is greater than the energy required to break the ionic lattice (lattice enthalpy). The net release of energy manifests as an increase in temperature of the solution.
9. Can you explain the difference between endothermic and exothermic hydration?
Hydration is almost always exothermic (releases energy) due to the favorable interaction between ions and water molecules. However, the term "endothermic hydration" is sometimes used to describe cases where the overall dissolution process is endothermic, even though the hydration step itself releases energy.
10. What role does lattice enthalpy play in the formation of coordination compounds?
Lattice enthalpy is crucial in the formation of coordination compounds. When a coordination compound forms from an ionic solid, the lattice enthalpy must be overcome. The energy released by the formation of coordinate bonds between the metal ion and ligands must exceed the lattice enthalpy for the reaction to be favorable.
11. What is lattice enthalpy, and why is it important in chemistry?
Lattice enthalpy is the energy required to completely separate one mole of a solid ionic compound into its gaseous ions. It's important because it helps us understand the strength of ionic bonds and predict the stability of ionic compounds. The higher the lattice enthalpy, the more stable the ionic compound.
12. How does the size of ions affect lattice enthalpy?
Ion size inversely affects lattice enthalpy. Smaller ions result in higher lattice enthalpy because they can get closer together, creating stronger electrostatic attractions. Larger ions lead to lower lattice enthalpy due to increased distance between charges and weaker attractions.
13. How does the charge of ions influence lattice enthalpy?
Ion charge has a significant impact on lattice enthalpy. Higher charges result in stronger electrostatic attractions between ions, leading to higher lattice enthalpies. For example, the lattice enthalpy of MgO (Mg2+ and O2-) is higher than that of NaCl (Na+ and Cl-) due to the higher charges involved.
14. What is the Born-Haber cycle, and how is it used in calculating lattice enthalpy?
The Born-Haber cycle is a thermodynamic cycle that relates various energy changes involved in the formation of an ionic compound from its elements. It's used to indirectly calculate lattice enthalpy by combining other measurable enthalpies, such as enthalpy of formation, ionization energy, and electron affinity, when direct measurement is not possible.
15. What is the relationship between lattice enthalpy and melting point of ionic compounds?
There's a positive correlation between lattice enthalpy and melting point. Compounds with higher lattice enthalpies require more energy to break their ionic bonds, resulting in higher melting points. This is why compounds like MgO have much higher melting points than NaCl.
16. Why are some ionic compounds soluble in water while others are not?
The solubility of ionic compounds depends on the balance between lattice enthalpy and hydration enthalpy. If the energy released by hydration (hydration enthalpy) exceeds the energy required to break the ionic bonds (lattice enthalpy), the compound will dissolve. If lattice enthalpy is greater, the compound remains insoluble.
17. How does temperature affect the solubility of ionic compounds?
Temperature generally increases the solubility of ionic compounds in water. This is because higher temperatures provide more thermal energy to overcome the lattice enthalpy. However, there are exceptions, such as gases dissolved in liquids, where solubility decreases with increasing temperature.
18. How does the concept of entropy relate to the dissolution of ionic compounds?
Entropy, which measures the disorder of a system, generally increases during dissolution as the ordered ionic lattice breaks apart into more randomly dispersed ions in solution. This increase in entropy often contributes favorably to the dissolution process, even in cases where the enthalpy change is slightly unfavorable.
19. What is meant by "like dissolves like" in the context of ionic compounds and solvents?
"Like dissolves like" refers to the principle that polar substances tend to dissolve in polar solvents, while non-polar substances dissolve in non-polar solvents. Ionic compounds, being highly polar, dissolve well in polar solvents like water due to favorable ion-dipole interactions, but poorly in non-polar solvents like hexane.
20. How does the concept of lattice enthalpy apply to the solubility product constant (Ksp)?
Lattice enthalpy indirectly affects the solubility product constant (Ksp). Compounds with higher lattice enthalpies tend to have lower solubilities and thus lower Ksp values. This is because more energy is required to break the strong ionic bonds, making the dissolution process less favorable.
21. How does the lattice enthalpy of a compound affect its reactivity?
Compounds with higher lattice enthalpies are generally less reactive because more energy is required to break the strong ionic bonds. This makes them more stable and less likely to participate in chemical reactions. Conversely, compounds with lower lattice enthalpies are often more reactive due to weaker ionic bonds.
22. What is the significance of Fajans' rules in predicting lattice enthalpy?
Fajans' rules help predict the degree of covalent character in predominantly ionic bonds. They state that small, highly charged cations and large, easily polarizable anions tend to form more covalent bonds. This increased covalency leads to higher lattice enthalpies than would be expected for purely ionic interactions.
23. How does the concept of lattice enthalpy apply to non-ionic compounds?
While lattice enthalpy is primarily associated with ionic compounds, the concept can be extended to molecular solids. In these cases, it represents the energy required to separate the molecules in the solid to the gas phase. However, the energies involved are typically much lower due to weaker intermolecular forces.
24. Why is it difficult to directly measure lattice enthalpy experimentally?
Direct measurement of lattice enthalpy is challenging because it involves the hypothetical process of separating a solid ionic compound into gaseous ions. This can't be done in a single step under normal laboratory conditions. Instead, indirect methods like the Born-Haber cycle are used to calculate lattice enthalpy.
25. How does the presence of crystal defects affect lattice enthalpy?
Crystal defects generally decrease lattice enthalpy because they introduce imperfections in the crystal structure. These imperfections weaken the overall ionic bonding in the lattice. Common defects include Schottky defects (missing ion pairs) and Frenkel defects (ions in interstitial positions).
26. Can you explain the concept of lattice energy density and its significance?
Lattice energy density is the lattice enthalpy per unit volume of the crystal. It's significant because it provides a way to compare the strength of ionic bonding across different compounds, accounting for differences in ion size. Higher lattice energy densities generally indicate stronger overall ionic bonding in the crystal.
27. How does the hydration enthalpy of an ion relate to its ability to act as a Lewis acid?
Ions with more negative hydration enthalpies often make stronger Lewis acids. This is because the strong interaction with water molecules (indicated by a more negative hydration enthalpy) suggests a greater ability to accept electron pairs from other species, which is the definition of a Lewis acid.
28. What is the connection between hydration enthalpy and the concept of hard and soft acids and bases (HSAB)?
Hydration enthalpy correlates with the HSAB concept. Hard acids and bases, which are typically small and highly charged, tend to have more negative hydration enthalpies. Soft acids and bases, which are larger and less charged, have less negative hydration enthalpies. This relationship helps predict the strength of acid-base interactions.
29. How does the concept of hydration enthalpy apply to non-aqueous solvents?
While hydration enthalpy specifically refers to interactions with water, the concept can be extended to other solvents as "solvation enthalpy." The principles are similar: ions with stronger interactions with the solvent molecules will have more negative solvation enthalpies. The magnitude and order of these enthalpies may differ from those in water.
30. Why do some compounds, like lithium chloride, absorb moisture from the air (hygroscopic behavior)?
Hygroscopic behavior is related to the balance between lattice enthalpy and hydration enthalpy. Compounds like LiCl are hygroscopic because the energy released by hydration of the ions is significantly greater than the lattice enthalpy. This makes the interaction with water molecules from the air energetically favorable.
31. How does the concept of hydration enthalpy relate to the formation of clathrate hydrates?
Clathrate hydrates form when water molecules create cage-like structures around guest molecules or atoms. The formation of these structures is driven by favorable hydration interactions, similar to those quantified by hydration enthalpy. The strength of these interactions influences the stability of the clathrate hydrate.
32. What is the relationship between lattice enthalpy and the solubility of ionic compounds in non-polar solvents?
Ionic compounds with high lattice enthalpies are generally less soluble in non-polar solvents. This is because non-polar solvents cannot provide sufficient energy (in the form of solvation) to overcome the strong ionic bonds. The lack of strong ion-solvent interactions makes the dissolution process unfavorable.
33. How does the concept of lattice enthalpy apply to the formation of solid solutions?
In solid solutions, atoms or ions of one element substitute for those of another in a crystal lattice. The feasibility of forming a solid solution depends partly on the difference in lattice enthalpies of the pure compounds. Smaller differences in lattice enthalpies generally favor the formation of solid solutions.
34. Can you explain the role of hydration enthalpy in ion exchange processes?
Hydration enthalpy plays a crucial role in ion exchange processes. Ions with more negative hydration enthalpies tend to bind more strongly to ion exchange resins due to their stronger interactions with water and polar groups on the resin. This affects the selectivity and efficiency of ion exchange processes.
35. How does the concept of lattice enthalpy relate to the strength of ionic conductivity in solids?
Lattice enthalpy generally has an inverse relationship with ionic conductivity in solids. Higher lattice enthalpies indicate stronger ionic bonds, making it more difficult for ions to move through the crystal lattice. Therefore, compounds with lower lattice enthalpies often exhibit better ionic conductivity.
36. What is the significance of hydration enthalpy in understanding the Gibbs free energy of solvation?
Hydration enthalpy is a key component of the Gibbs free energy of solvation. While hydration enthalpy represents the enthalpy change of the solvation process, the Gibbs free energy also includes the entropy change. Understanding hydration enthalpy helps predict whether a solvation process will be spontaneous (negative Gibbs free energy).
37. How does the concept of lattice enthalpy apply to the phenomenon of deliquescence?
Deliquescence occurs when a substance absorbs so much water from the atmosphere that it dissolves into a solution. This happens when the combined lattice enthalpy and entropy change of dissolution is overcome by the hydration enthalpy and entropy increase of the dissolved ions. Compounds with lower lattice enthalpies are more prone to deliquescence.
38. Can you explain the relationship between hydration enthalpy and the concept of salting-in and salting-out of proteins?
Hydration enthalpy relates to salting-in and salting-out effects on proteins. Ions with more negative hydration enthalpies (kosmotropes) tend to salt-out proteins by competing for water molecules, while ions with less negative hydration enthalpies (chaotropes) tend to salt-in proteins by increasing their solubility.
39. How does the concept of lattice enthalpy apply to the formation of intercalation compounds?
In the formation of intercalation compounds, guest species are inserted between layers of a host lattice. The process must overcome part of the lattice enthalpy of the host. Successful intercalation occurs when the energy released by the new interactions (between guest and host) compensates for the partial disruption of the original lattice.
40. What is the significance of hydration enthalpy in understanding the solvation of gases in water?
Hydration enthalpy helps explain the solvation behavior of gases in water. Gases with stronger interactions with water molecules (more negative hydration enthalpies) tend to be more soluble. This is why polar gases like HCl are generally more soluble in water than non-polar gases like N2.
41. How does the concept of lattice enthalpy relate to the formation of superionic conductors?
Superionic conductors are solids with unusually high ionic conductivity. They often have relatively low lattice enthalpies for at least one ion species, allowing these ions to move easily through the crystal structure. The balance between maintaining overall structural integrity (higher lattice enthalpy) and allowing ion mobility (lower lattice enthalpy for mobile ions) is crucial for superionic behavior.
42. Can you explain the role of hydration enthalpy in the phenomenon of ion pairing in solution?
Hydration enthalpy influences ion pairing in solution. Ions with less negative hydration enthalpies are more likely to form ion pairs because they interact less strongly with water molecules. Conversely, ions with more negative hydration enthalpies tend to remain fully dissociated due to strong interactions with the solvent.
43. How does the concept of lattice enthalpy apply to the design of solid electrolytes for batteries?
In designing solid electrolytes, a balance of lattice enthalpy is crucial. The material must have sufficient lattice enthalpy to maintain structural integrity, but low enough to allow for ion mobility. Compounds

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