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Enthalpies for Different Types of Reaction

ChemistryChemical ThermodynamicsFor NEET aspirants

The enthalpy change of a reaction is the heat absorbed or released at constant pressure - the most useful energy quantity for chemistry because most reactions occur in open vessels at atmospheric pressure. This concept covers the definition , the crucial relation for gaseous reactions, and every important type of enthalpy tested in JEE and NEET: enthalpies of formation, combustion, neutralization, ionization, hydration, solution, precipitation, transition, and phase transitions. It also covers Kirchhoff's equation for the temperature dependence of .

Key Formulas - Quick Reference
  1. Enthalpy:
  2. At constant pressure, ; at constant volume,
  3. For gaseous reactions: where (moles of gaseous products) - (moles of gaseous reactants)
  4. Enthalpy of reaction from formation enthalpies:
  5. Neutralization of strong acid + strong base: (approx )
  6. Enthalpy of ionization:
  7. Kirchhoff's equation: ; similarly

1. Enthalpy of a system

Most chemical reactions occur at constant atmospheric pressure. Under constant pressure, the heat exchanged equals a state-function quantity called the enthalpy:

(definition of enthalpy)

Since , and are state functions, is also a state function and an extensive property. Like , absolute enthalpy cannot be measured; only changes can.

Relation between and

Differentiating :

For a chemical reaction involving gases, at constant temperature , where is the change in moles of gaseous species. Hence:

For reactions in condensed phases (only solids and liquids), and so .

Exothermic vs endothermic

Enthalpy diagrams for exothermic and endothermic reactions Two side-by-side enthalpy versus progress-of-reaction diagrams. Left panel shows an exothermic reaction: reactants sit on a higher plateau, the curve rises to a peak marking the activation energy, then falls to a lower products plateau. A blue arrow labeled Delta H less than zero points downward between the two plateaus, showing energy released. Right panel shows an endothermic reaction: reactants sit on a lower plateau, the curve rises to a higher peak, then falls to a products plateau higher than reactants but below the peak. A blue arrow labeled Delta H greater than zero points upward between the two plateaus, showing energy absorbed. In both panels a pink dashed arrow marks the activation energy from the reactants plateau up to the peak. Exothermic (ΔH < 0) Enthalpy (H) Progress of reaction Reactants Products Activation energy ΔH < 0 energy released Endothermic (ΔH > 0) Enthalpy (H) Progress of reaction Reactants Products Activation energy ΔH > 0 energy absorbed
Figure: Enthalpy versus progress of reaction. Exothermic (left): products sit lower than reactants; the reaction releases heat and . Endothermic (right): products sit higher than reactants; the reaction absorbs heat and . In both cases the pink arrow marks the activation energy - the minimum energy needed to reach the transition state at the peak.
  • Exothermic: , so . Heat is released. Examples: combustion, neutralization.
  • Endothermic: , so . Heat is absorbed. Examples: melting of ice, decomposition of CaCO.
Solved Example 1
For the reaction , express the relation between and .
Solution:

Gaseous moles: reactants , products (water is liquid).

.

.

2. Standard states and standard enthalpy

Since enthalpies depend on temperature and pressure, chemists agree on reference conditions called the standard state:

  • Gas: ideal gas at partial pressure at the specified temperature.
  • Liquid: pure liquid at pressure at the specified temperature.
  • Solid: pure crystalline solid at pressure at the specified temperature.
  • Solution species: solute at (approximately ) at .

The specified temperature is usually (C). Enthalpies measured at standard state are denoted with a superscript circle, e.g. .

3. Enthalpy of formation

The standard enthalpy of formation of a compound is the enthalpy change when one mole of the compound is formed from its constituent elements in their most stable states at standard conditions.

By convention: (element in its stable state) .
So , , , , but .

Examples of formation reactions:

Enthalpy of reaction from formation enthalpies

where is the stoichiometric coefficient in the balanced equation.

Solved Example 2
Calculate the standard enthalpy of the reaction . Given , , .
Solution:

4. Enthalpy of combustion

The enthalpy of combustion is the enthalpy change when one mole of a substance undergoes complete combustion with oxygen at standard conditions, giving products in their stable states.

Combustion is always exothermic, so is always negative.

Examples:

Uses. Enthalpies of combustion are experimentally accurate and widely tabulated. They are used to (i) calculate calorific values of fuels, (ii) calculate enthalpies of formation of hydrocarbons (which cannot be measured directly).

5. Enthalpy of neutralization

The enthalpy of neutralization is the enthalpy change when one gram-equivalent of an acid is neutralized by one gram-equivalent of a base in dilute solution to form one mole of water:

Why is it constant for strong acid + strong base?

Both strong acids and strong bases dissociate completely in dilute solution. The only chemical change is the combination of and to form water - which is the same regardless of the identity of the strong acid or base. Hence the enthalpy change is a constant.

Weak acids and bases: enthalpy of ionization

For a weak acid (or base), some heat is absorbed during ionization of the weak acid, so the net heat released on neutralization is less than . The difference gives the enthalpy of ionization of the weak acid or base.

Two-step picture: Ionization: , (positive)
Neutralization: ,
Overall: ,

Example: , .

Hence .

Solved Example 3
Enthalpy of neutralization of HCl by NaOH is and by NHOH is . Calculate the enthalpy of dissociation of NHOH.
Solution:

Split the neutralization of NHOH into ionization + neutralization:

(i)

(ii)

Total:

6. Enthalpy of hydration

Hydration enthalpy is defined in two closely related ways:

(a) Hydration of anhydrous or partially hydrated salt

The enthalpy change when one mole of an anhydrous salt combines with the requisite moles of water to form a stable hydrated salt.

Example:

(b) Hydration of gaseous ions

The enthalpy change when one mole of a gaseous ion dissolves in a large amount of water to form the aqueous ion:

By convention, , which lets us tabulate hydration enthalpies of all other ions.

7. Enthalpy of solution

The integral enthalpy of solution is the enthalpy change when one mole of solute dissolves in a definite amount of solvent to give a solution of specified concentration.



(infinite dilution)

When the amount of solvent is not specified, it is taken to be very large (infinite dilution).

8. Enthalpy of transition

The enthalpy change when one mole of a substance is transformed from one allotropic form to another at standard conditions:

Solved Example 4
Calculate the enthalpy of transition of diamond to graphite from the following data:

Solution:

Subtracting the second from the first:

Reversing:

9. Phase transition enthalpies

Enthalpy changes accompanying phase transitions at constant and :

TransitionSymbolDirectionSign of
Fusion (melting)solid liquidpositive (endothermic)
Vaporizationliquid gaspositive (endothermic)
Sublimationsolid gaspositive (endothermic)
Freezing (solidification)liquid solidnegative (exothermic)
Condensationgas liquidnegative (exothermic)

These are connected by Hess's law: .

10. Enthalpy of atomization

The enthalpy of atomization is the enthalpy change when one mole of a substance is completely dissociated into isolated gaseous atoms.

For a diatomic gas like : (same as bond dissociation enthalpy in this case).

For a solid: (same as enthalpy of sublimation for a monoatomic solid).

11. Enthalpy of precipitation

The enthalpy change when one mole of a precipitate forms in solution:

12. Enthalpy of ionization (for weak acids/bases)

Already introduced under neutralization - the enthalpy change when one mole of a weak electrolyte ionizes completely in dilute solution.

The larger the enthalpy of ionization, the weaker the acid or base.

13. Enthalpy of formation of ions

The enthalpy change when one mole of gaseous ions is obtained from elements in their standard state:

By convention , which lets us tabulate the enthalpies of formation of all other ions.

Solved Example 5
The enthalpy of formation of is and enthalpy of neutralization of a strong acid and a strong base is . What is the enthalpy of formation of ions?
Solution:

Neutralization:

Using convention :

14. Kirchhoff's equation: variation of with temperature

Enthalpies of individual substances depend on temperature (higher gives higher ), so the enthalpy change of a reaction also varies with temperature. Consider :

At :

At :

The temperature dependence of enthalpy for each species: .

Kirchhoff's equation: At constant volume:

If is temperature-dependent, use the integral form: .

Solved Example 6
The standard heat of formation of gaseous NH is at . Given the constant-pressure molar heat capacities of , and are respectively , find at for .
Solution:

at , want at .

Kirchhoff:

15. Common Mistakes to Avoid

Watch out
  • Applying to reactions with no gaseous species. counts only gaseous moles - ignore solids and liquids.
  • Forgetting the stoichiometric coefficients. uses - so if the equation has , use .
  • Confusing enthalpy of formation with enthalpy of combustion. Formation forms the compound from elements. Combustion burns the compound in oxygen.
  • Assuming enthalpy of neutralization is always . Only strong acid + strong base gives this constant value. Weak acid or weak base neutralizations release less heat.
  • Forgetting that of an element in its stable form is zero. But of an allotrope that is not the standard form is not zero (e.g. diamond, monoclinic sulphur).
  • Ignoring the phase symbols in enthalpy problems. . Always check the phase.

Frequently Asked Questions

Q1. Why is enthalpy more useful than internal energy for chemistry problems?

Most laboratory reactions occur in open vessels at constant atmospheric pressure. At constant pressure, the heat absorbed equals , not . So is what a coffee-cup calorimeter directly measures, and it is the thermodynamic quantity most closely tied to reactions as we actually run them.

Q2. When is equal to ?

When there is no change in the number of moles of gas (), then . This includes reactions between only solids and liquids, and gaseous reactions where the moles of gas are unchanged (e.g. ).

Q3. Why is the enthalpy of formation of an element in its stable state taken as zero?

It is a convention chosen so that absolute enthalpies (which cannot be measured) drop out of calculations. The differences of formation enthalpies are what matter physically, and this convention gives self-consistent, tabulated values for all compounds.

Q4. Why is neutralization of a strong acid by a strong base always ?

Both strong acids and strong bases are fully ionized in dilute solution. The only chemical change is , which is identical regardless of which strong acid and strong base were used. Hence the enthalpy change is the same, approximately .

Q5. Why is neutralization of a weak acid by a strong base less exothermic?

A weak acid is not fully ionized in solution; some energy is consumed to ionize it. The heat released on neutralization is therefore the standard minus the energy spent on ionization. The stronger the weak acid, the smaller its ionization enthalpy, and the closer the neutralization heat is to .

Q6. What is the enthalpy of atomization and how is it different from bond dissociation energy?

Enthalpy of atomization is the total energy needed to break all bonds and separate one mole of substance into gaseous atoms. For a diatomic gas like , this equals the bond dissociation energy of the H-H bond. But for polyatomic molecules, atomization means breaking every bond, giving a sum of average bond enthalpies.

Q7. Why does the enthalpy of a reaction depend on temperature?

Enthalpies of individual substances rise with temperature according to their heat capacities . If products and reactants have different heat capacities (), the enthalpy change of the reaction also depends on temperature. Kirchhoff's equation quantifies this: .

Q8. What is the difference between integral and differential enthalpy of solution?

Integral enthalpy of solution is the heat change when one mole of solute dissolves in a specified amount of solvent to give a solution of stated concentration. Differential (or partial molar) enthalpy of solution is the heat change per mole of solute added to a very large volume of an existing solution, so that its concentration essentially does not change. In JEE/NEET, "enthalpy of solution" almost always means the integral version at high dilution.

Previous year questions on Enthalpies for Different Types of Reaction

5 questions from past papers, each with a step-by-step solution.

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