Why is the Enthalpy of the NO2 to N2O4 Reaction Exothermic?

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SUMMARY

The reaction of nitrogen dioxide (NO2) dimerizing to form dinitrogen tetroxide (N2O4) is exothermic due to the formation of a stable N-N bond, which reduces the overall energy of the system. The nitrogen dioxide molecule, characterized by its radical and positive formal charge, is less stable compared to the larger dinitrogen tetroxide, which has a lower charge density. The enthalpy change can be calculated using standard enthalpy values, confirming that the reaction releases energy as the product is more stable than the reactants.

PREREQUISITES
  • Understanding of chemical bonding and stability, particularly in nitrogen compounds.
  • Familiarity with enthalpy concepts and exothermic vs. endothermic reactions.
  • Knowledge of formal charge calculations in molecular structures.
  • Basic grasp of hybridization, specifically sp2 hybridization in nitrogen dioxide.
NEXT STEPS
  • Calculate the enthalpy change for the reaction using standard enthalpy values.
  • Research the concept of charge density and its impact on molecular stability.
  • Explore the role of hybridization in determining molecular reactivity and stability.
  • Investigate the thermodynamic principles governing exothermic reactions in general.
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Chemistry students, educators, and anyone interested in thermodynamics and reaction mechanisms, particularly those studying nitrogen compounds and enthalpy changes.

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Homework Statement



Determine the enthalpy of this reaction (below).

2NO_{2} \rightarrow N_{2}O_{4}

Homework Equations



Reaction is exothermic if product is more stable than reactants.

Reaction is endothermic if the reverse were true (product less stable than reactants).

The Attempt at a Solution



I'm trying to think of all the different ways I can explain why the forward reaction is exothermic.

1) Dimerization of nitrogen dioxide; a N-N bond is being formed using the radical on the nitrogen in nitrogen dioxide.

2) The radical on the nitrogen in nitrogen dioxide makes it inherently less stable than a molecule with no radicals.

3) The nitrogen dioxide has a positive formal charge on the nitrogen and a negative formal charge on its oxygen. Positive formal charges are also present on the nitrogens in nitrogen tetraoxide along with negative formal charges on two oxygens but the entire molecule is bigger, so the charge density is likely lower.

4) Hybridization? The nitrogen of the nitrogen dioxide is sp2 hybridized (do radicals count when determining hybridization)?

Anything else I can consider in explaining why the above reaction is exothermic?
 
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It's not really clear what you are asking.

The problem statement wants you to calculate the enthalpy value. Have you done that, and now you are basically looking for some intuitive reasoning to make sense of the result, to satisfy your own curiosity? Or is coming up with the reason actually part of the assignment, even though the problem statement does not explicitly ask for a reason?

(Sorry I can't actually help with coming up with the reason. But as nobody else has replied in 2 days, I just thought I'd try to get some clarification for the benefit of others who may be better able to help.)
 
Just really want to know.
It's the former. I know the enthalpies but why? Prof didn't give satisfying explanation.
 

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