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Entropy and Gibbs

Notes chemistry

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32 views7 pages

Entropy and Gibbs

Notes chemistry

Uploaded by

Admire NLEYA
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Reaction Feasibility

Reaction Feasibility

 The Gibbs equation can be used to calculate whether a reaction is feasible or not

θ θ θ
Δ G =Δ H reaction−T Δ S system

 When Δ Gθ is negative, the reaction is feasible and likely to occur


 When Δ Gθ is positive, the reaction is not feasible and unlikely to occur
 Feasible and spontaneous are fairly similar terms to describe reactions
o Feasible tends to be used to describe reactions which are energetically
favourable, so reactions that should go
o Spontaneous tends to be used to describe reactions that go of their own accord

Summary for temperature and Gibbs free energy

Worked example
Determining the feasibility of a reaction Calculate the Gibbs free energy change for
the following reaction at 298 K and determine whether the reaction is feasible.

2Ca (s) + O2 (g) → 2CaO (s) ΔH = -635.5 kJ mol-1


θ −1 −1
S [Ca(s)]=41.00 J K mol
θ
S [O2(g)] = 205.0 J K-1 mol-1
θ
S [CaO(s)] = 40.00 J K-1 mol-1

Answer

Step 1: Calculate Δ S θ system


θ θ θ
Δ S ystem=Σ Δ S products−Δ S Σreactant s
θ θ θ θ
Δ S system=(2 x Δ S [CaO (s)])−(2 x Δ S [Ca( s)]+ Δ S [O2( g)])

= (2 x 40.00) - (2 x 41.00 + 205.0)

= -207.0 J K-1 mol-1

Step 2: Convert Δ S θ to kJ K-1 mol-1

= -207.0 J K-1 mol-1÷ 1000 = -0.207 kJ mol-1

Step 3: Calculate Δ Gθ
θ θ θ
Δ G =Δ H reaction−T Δ S syste m

= -635.5 - (298 x -0.207)

= -573.8 kJ mol-1

Step 4: Determine whether the reaction is feasible

Since the Δ Gθ is negative the reaction is feasible

Reaction Feasibility: Temperature Changes

 The feasibility of a reaction can be affected by the temperature


 The Gibbs equation will be used to explain what will affect the feasibility of a reaction for
exothermic and endothermic reactions
Exothermic reactions

 In exothermic reactions, Δ H θ reaction is negative


 If the Δ S θ systemis positive:
o Both the first and second term will be negative
o Resulting in a negative Δ G θ so the reaction is feasible
o Therefore, regardless of the temperature, an exothermic reaction with a positive
θ
Δ S system will always be feasible
 If the Δ S θ system is negative:
o The first term is negative and the second term is positive
o At very high temperatures, the -T Δ S θ system will be very large and positive and
will overcome Δ H θ reaction
o Therefore, at high temperatures Δ G θ is positive and the reaction is not feasible
 Since the relative size of an entropy change is much smaller than an enthalpy change, it
is unlikely that TΔS > ΔH as temperature increases
 These reactions are therefore usually spontaneous at normal conditions

The diagram shows under which conditions exothermic reactions are feasible

Endothermic reactions

 In endothermic reactions, Δ H θ reaction is positive


 If the Δ S θ system is negative:
o Both the first and second term will be positive
o Resulting in a positive Δ Gθ so the reaction is not feasible
o Therefore, regardless of the temperature, endothermic with a negative
θ
Δ S system will never be feasible
θ
 If the Δ S system is positive:
o The first term is positive and the second term is negative
o At low temperatures, the -T Δ S θ system will be small and negative and will not
overcome the larger Δ H θ reaction
o Therefore, at low temperatures Δ Gθ is positive and the reaction is not feasible
o The reaction is more feasible at high temperatures as the second term will
become negative enough to overcome the Δ H θ reaction resulting in a negative
θ
ΔG
 This tells us that for certain reactions which are not feasible at room temperature, they
can become feasible at higher temperatures
o An example of this is found in metal extractions, such as the extraction if iron in
the blast furnace, which will be unsuccessful at low temperatures but can occur
at higher temperatures (~1500 oC in the case of iron)

The diagram shows under which conditions endothermic reactions are feasible

A summary table of free energy conditions


Free Energy Vs Temperature Graphs

 Rearranging the Gibbs equation allows you to determine the temperature at which a
non-spontaneous reaction become feasible

θ θ θ
Δ G =Δ H reaction−TΔ S system

 For a reaction to be feasible Δ Gθ must be zero or negative

θ θ θ
Δ G =Δ H −T Δ S
θ θ
Δ H =T Δ S
θ θ
T =Δ H / Δ S

Worked example
At what temperature will the reduction of aluminium oxide with carbon become
spontaneous?
θ
Al2O3(s) + 3C(s) → 2Al(s) + 3CO(g) Δ H = +1336 kJ mol-1
θ
Δ S =+581 J K −1 mol−1

Answer:

If Δ Gθ = 0 then , T = Δ H θ / Δ S θ

T = 1336 ÷ (581/1000)

T = 2299 K

Graphing the Gibbs Equation

 The Gibbs equation can be expressed as the equation for a straight line
θ θ θ
Δ G =Δ H −T Δ S
θ θ θ
Δ G =−T Δ S + Δ H

y = mx + c

 A graph of free energy versus temperature (in K) will give a straight line, with slope - Δ S θ
and y-intercept, .
 The variation of Δ Gθ against T for the synthesis of ammonia has been plotted below:

N2 (g) + 3H2 (g)⇌ 2NH3 (g)

Graph of free energy versus temperature for the synthesis of ammonia

 From this graph you should be able to see some key features:
o The x-intercept shows you where the reaction ceases to be spontaneous, in this
case at 460 K (187 oC)
o Above this temperature ΔGꝋ is positive so the reaction is not feasible
 However, you may recall that the operating conditions of the Haber
process are higher than this temperature, but this graph takes no account
of the use of a catalyst which affects the energetics of the system, nor
does it take into account anything about the rate of reaction or the fact
that it is an equilibrium and removal of the ammonia as soon as it is
formed also tips the balance in favour of the product
o The y-intercept shows you reaction is exothermic which you can see from the
enthalpy of formation; the value is approximately -46 kJ mol -1
o An exothermic equilibrium reaction would be favoured by lower temperatures -
this is seen by the value of Δ Gθ becoming increasingly negative as the
temperature falls

Exam Tip
You will notice that the line on the graph does not continue below 240 K. The simple
reason for this is that at this point the ammonia will have reached it boiling point and so
the gradient would change because it is now liquid ammonia.

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