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What is a spontaneous reaction?

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Entropy

Entropy is a measure of disorder, and is given the

symbol S. The units of S are: J K–1 mol–1.

 ordered  disordered
 regular arrangement  random arrangement
of particles of particles
 low entropy  high entropy
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Entropy change for reactions

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Predicting entropy changes

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Calculating entropy changes
Standard entropy changes for any chemical reaction or
physical change can be calculated using the following simple
expression:

DS = SSөproducts – SSөreactants

Remember the following points:

 the units of entropy, S, are J K–1 mol–1

 entropies of elements are not zero like DHf values, so they

should be included in calculations.

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Calculating entropy changes

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Entropy change calculations

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Entropy changes in the surroundings

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Entropy changes in the surroundings

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Gibbs free energy
Whether a reaction is spontaneous depends on:

 the entropy change of the system

 the enthalpy change of the system

 the temperature.

The change in a quantity called the Gibbs free energy

provides a measure of whether a reaction is spontaneous.
The Gibbs free energy change is given the symbol DG and
can be calculated for a reaction using the expression:

DG = DH – TDS A reaction will be spontaneous if DG < 0.

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How to calculate ∆G

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Calculating ∆G

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Feasibility of reactions
Even if DG is positive at room temperature, there may be a
higher temperature at which a reaction becomes feasible.

DG = DH – TDS

If DS is positive, there may be a point at which TDS is big

enough to outweigh the enthalpy factor.
DH DS As temp. increases… Feasible?
yes, above a
positive positive makes TDS > DH
certain temp.
negative positive makes DG more negative always
positive negative no effect: DG always positive never
negative negative unlikely to make TDS > DH usually

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Finding the temperature
Consider the reduction of aluminium oxide with carbon:

Al2O3(s) + 3C(s) 2Al(s) + 3CO(g)

DH = +1336 kJ mol–1 DS = +581 J K–1 mol–1

As both DH and DS are positive, DG will become negative if

TDS > DH.

The temperature at which this reaction becomes feasible

can be calculated. This will be when DG = 0.

If DG = 0, then T = DH / DS

T = 1336 / (581/1000)

T = 2299 K
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When is a reaction feasible?

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 Solubility

When an ionic solid dissolves into water, this process can

be either exothermic or endothermic.

Thinking about dissolving as an energy cycle:

∆H solution = lattice dissociation enthalpy + hydration enthalpy

The hydration enthalpy is the enthalpy change

when 1 mole of gaseous ions dissolve in
sufficient water to give an infinitely dilute solution.
Hydration enthalpies are always negative.

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 Solubility

The size of the hydration enthalpy is governed by the

amount of attraction between the ions and the water
molecules:
The attractions are stronger the smaller the ion. For
example, hydration enthalpies fall as you go down a
group in the Periodic Table. The small lithium ion has by
far the highest hydration enthalpy in Group1, and the
small fluoride ion has by far the highest hydration
enthalpy in Group 7. In both groups, hydration enthalpy
falls as the ions get bigger.
The attractions are stronger the more highly charged the
ion. For example, the hydration enthalpies of Group 2
ions (like Mg2+) are much higher than those of Group 1
ions (like Na+).
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Solubility
In the same way that reactions are only feasible if DG < 0, a
substance will be soluble in water at a specific temperature
if DGsol < 0.

DGsol = DHsol – TDSsol

DHsol DSsol DG / feasibility

feasible if T is large enough to make
positive positive
DG negative
negative positive always feasible
positive negative never feasible
usually feasible (T is unlikely to be
negative negative
large enough to make DG positive)

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Solubility
For example:

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Solubility

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Solubility

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Thermodynamics vs. kinetics
Just because a reaction is spontaneous does not mean that it
appears to happen. It may be that the reaction is so slow or has
such a high activation energy that it is not generally observed.
Consider the reaction involving the combustion of carbon:

C(s) + O2(g) CO2(g)

DH = –394 kJ mol–1 DS = +3 J K–1 mol–1

This reaction has a negative value for DG, so is feasible, but a
piece of carbon does not spontaneously burn if left on the
table. Energy would need to be put in for the reaction to begin.
A reaction that is thermodynamically feasible is not necessarily
kinetically feasible.

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http://web.tock.com/kalee/chem32/
kinT/

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