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BOND ENERGIES - Entropy-Free Energy

1) Bond energies (BDE) refer to the energy required to break bonds between atoms in diatomic molecules. BDE values can be used to calculate enthalpy changes (ΔH) of reactions using Hess's law. 2) Entropy (S) is a measure of disorder and the change in entropy (ΔS) is related to the change in enthalpy (ΔH) by the second law of thermodynamics. 3) The free energy change (ΔG) of a reaction accounts for both enthalpy (ΔH) and entropy (TΔS) changes. For a reaction to be spontaneous, ΔG must be negative under standard conditions.

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67 views3 pages

BOND ENERGIES - Entropy-Free Energy

1) Bond energies (BDE) refer to the energy required to break bonds between atoms in diatomic molecules. BDE values can be used to calculate enthalpy changes (ΔH) of reactions using Hess's law. 2) Entropy (S) is a measure of disorder and the change in entropy (ΔS) is related to the change in enthalpy (ΔH) by the second law of thermodynamics. 3) The free energy change (ΔG) of a reaction accounts for both enthalpy (ΔH) and entropy (TΔS) changes. For a reaction to be spontaneous, ΔG must be negative under standard conditions.

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Oluwatosin Osisanya
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© © All Rights Reserved
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BOND ENERGIES

Atoms are held together in molecules by chemical bonds. Energy required to break the bond that
holds two atoms together in a diatomic molecule is called Bond Energies (BDE) (kJ/mol of
bonds).

E.g. H−H (g ) → 2 H ( g ) ∆ H =+435 kJ


Cl−Cl (g ) → 2Cl ( g) ∆ H=+243 kJ

H−Cl ( g) → H ( g )+Cl( g) ∆ H=+ 431 kJ

Each of these ΔH values is positive, indicating that the energy is absorbed in each process.
If any of these equations is reversed, ΔH will be negative which implies that energy is released
when a bond is formed – the same amount of energy required to break the bond.
E.g. H (g) +Cl (g ) → HCl( g) ∆ H=−431 kJ

BDE may be used to determine some ΔHs of reactions e.g.


H 2 (g) +Cl2 (g) →2 H Cl(g)
{BDE : H −H=+ 435 kJ ; Cl−Cl=+243 kJ ; H −Cl=+ 431 kJ }
We can use the Hess’s law by assuming the equations for the bond dissociation in the molecules
and bond formation in HCl to get ΔH as:
H−H (g ) → 2 H ( g ) ∆ H =+435 kJ

Cl−Cl (g ) → 2Cl ( g) ∆ H=+243 kJ

2 H (g ) +2Cl ( g) →2 H−Cl ( g) ∆ H=2 (−431 ) kJ =−862 kJ

Sum the equations gives: H−H (g )+ Cl−Cl ( g) →2 H−Cl ( g) ∆ H=−184 kJ

Assignment
N 2 (g) +O2(g ) → 2 N O(g)

[BDE: N−N =+941 kJ ,O−O=+494 kJ , N−O=+627 kJ ]

Note: ΔH values calculated in those two examples are 2x∆ H of of HCl(g) and NO(g) respectively
since the overall equation refers to the formation of two moles of these substances from their
elements in their standard states.
ΔH for a reaction can be derived from the relation:
∆ H =∑ BD Ereactants −∑ BD E products

This method can be extended to polyatomic molecules e.g. H2O, CH4, NH3, etc
Consider the dissociation of H2O as:
H−O−H ( g) →2 H (g ) +O (g ) ∆ H=+926 kJ

The energy required to break each H−O bond in H−O−H is the average of +926 kJ = +926/2
= +463 kJ/mol. This is called the average bond energy.
Note that: the strength of a bond in a molecule depends upon the structure of the entire molecule.
Consequently, the bond energy of a given type of bond is not the same in all molecules
containing such bond. E.g. the bond energy of H-O bond in a H-O-H molecule is different from
the bond energy of H-O in H-O-Cl molecule. Therefore, many bond energies are approximations
and ΔH value obtained by using these values must be regarded as estimate.

ENTROPY, FREE ENERGY AND SPONTANEITY OF REACTIONS


Entropy is the degree of disorderliness of a system. It is denoted by S. The change in entropy is
denoted by ΔS.
Entropy change, ΔS, is related to enthalpy change, ΔH, as:
∆H
∆ S>
T
(From the second law of thermodynamics)
Therefore, ΔH –TΔS < 0 for a spontaneous reaction.
The term ΔH –TΔS is defined as the free energy change (ΔG).
Thus, ∆ G=∆ H−T ∆ S
When these quantities are measured at certain standard states: pure solids and liquids, 1 atm, 1M
at 25⁰C, they are referred to as standard state data, ΔG⁰, ΔH⁰, ΔS⁰.
ΔG⁰ is a criterion for spontaneity
ΔG⁰ < 0 implies spontaneous reaction
ΔG⁰ > 0 implies non-spontaneous reaction
ΔG⁰ = 0 implies equilibrium mixture

ΔG⁰ are tabulated for the formation of substances just like ∆ H of .e.g. ∆ G of .
o o
∆ Greaction can be calculated from ∆ G f of reactants and products.
Example
Estimate ΔG for the combustion of 1 mole of ethanol if ΔGof : C2H5OH = -174.8 kJ/mol; O2 = 0
kJ/mol; CO2 = -394.4 kJ/mol; H2O(g) = -228.6 kJ/mol.
Solution
C2H5OH + 3O2 → 2CO2 + 3H2O; ΔG⁰ = ?
ΔG⁰ = ΔG⁰f(products) - ΔG⁰f(reactants) = 2(-394.4) + 3(-228.6) – (-174.8) -788.8 – 685.8 + 174.8
= -1299.8 kJ

FREE ENERGY AND EQUILIBRIUM CONSTANT


One of the most important equations of chemical thermodynamics relates ΔG⁰ and K:
∆ G °=−RTlnk
For electrochemical reactions, ΔG⁰ is related to the electromotive force (E⁰) as:
∆ G °=−nFE°
And
nFE °=RTlnK
Therefore,
RT
E °= lnK
nF
Where n is the number of electrons transferred in the overall cell equation.

Exercise
Calculate the equilibrium constant K for the reaction;
2+ ¿¿
2+ ¿+ Sn( aq) ¿
4 +¿↔ Fe(aq) ¿
Fe(s) + Sn(aq)

With E⁰ = 0.56 V at 25⁰C

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