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Q3.22:
What is the basic difference between the terms electron gain enthalpy and electronegativity?

Solution :

Step 1: Definition and Theoretical Framework of Electron Gain Enthalpy

Electron Gain Enthalpy ($\Delta_{eg}H$) is a thermodynamic quantity that measures the change in enthalpy when an electron is added to a neutral gaseous atom to form a negative ion (anion). It is defined by the following chemical equation:

$X(g) + e^- \rightarrow X^-(g); \quad \Delta_{eg}H$

[Per the First Law of Thermodynamics, this represents the energy released (exothermic) or absorbed (endothermic) during the process.]

  • Nature: It is an experimental property of an isolated gaseous atom.
  • Units: Measured in $kJ \cdot mol^{-1}$ or $eV \cdot atom^{-1}$.

Step 2: Definition and Theoretical Framework of Electronegativity

Electronegativity ($\chi$) is a dimensionless property representing the relative tendency of an atom in a chemical compound to attract a shared pair of electrons toward itself. Unlike electron gain enthalpy, it is not a direct measure of energy but rather a relative scale.

[Per the Pauling or Mulliken scales, $\chi$ is a property of an atom specifically when bonded within a molecule.]

  • Nature: It is a qualitative, relative numerical value assigned to elements.
  • Units: Dimensionless (Pauling scale).

Step 3: Comparative Analysis

Feature Electron Gain Enthalpy Electronegativity
System Isolated gaseous atom Atom in a bonded molecule
Physical Quantity Energy change ($kJ \cdot mol^{-1}$) Relative attraction tendency (No units)
Focus Quantitative measurement Qualitative comparison
Changeable Constant for a specific element in isolation Variable depending on the bonded partner

Step 4: Visualizing the Difference

Atom (g) + e- (Energy out) Bonded pair attraction

Step 5: Synthesized Conclusion

The fundamental distinction lies in the state of the atom. Electron gain enthalpy is a quantitative energy measurement of an isolated atom's ability to "accept" an incoming electron into its valence shell. Electronegativity is a relative, qualitative measure of an atom's ability to "pull" shared electrons toward itself within the context of a covalent bond. Consequently, an atom can have high electronegativity even if it has a low or positive electron gain enthalpy (e.g., noble gases, if induced), as the definitions govern different chemical scenarios.

Final Solution: Electron gain enthalpy is the energy change associated with the addition of an electron to an isolated gaseous atom, whereas electronegativity is a relative, dimensionless measure of an atom's tendency to attract shared bonding electrons toward itself in a molecule.


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