Lesson 18
Reactivity 1.4.3—At constant pressure, a
change is spontaneous if the change in
Gibbs energy, ΔG, is negative. (HL)
Interpret the sign of ΔG calculated from
thermodynamic data.
Determine the temperature at which a reaction
becomes spontaneous.
The Effect of Changing the Temperature - MATHS
◎ In the previous example:
○
○ ΔG = -101 kJ mol-1, ΔHo = -137 kJ mol-1, ΔSo = -121 J K-1 mol-1, T = 298 K
ΔG = ΔH - TΔS
◎ What happens if we increase the temperature?
○ Since ΔH and both ΔS are both negative, ΔG can be either positive or negative
depending on the temperature
◉ A high temperature will make the ʻTΔSʼ term large enough to counter-balance
the ΔH term making ΔG positive (non-spontaneous)
◉ At lower temperatures, the reaction will be spontaneous as ΔG is negative
● This does not mean that the reaction will be fast, just that it will (in theory)
happen
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At which temperature does the reaction become
spontaneous?
◎ This slide just explains the maths behind working out when the reaction
becomes spontaneous.
◎ The transition from spontaneous to non-spontaneous happens at ΔG = 0, so if
we use this we can determine the temperature necessary for this as follows:
ΔG = ΔH - TΔS : The initial equation
0 = ΔH - TΔS : Set ΔG = 0
TΔS = ΔH : Rearrange to make T subject
T = ΔH/ΔS
T = -137 / (-121/1000) : Substitute in values from previous slide
T = 1132 K : Evaluate
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Summarising the Effect Of Temperature Changes
∆H ∆S Spontaneity
Positive Positive Spontaneous at higher temperatures
Non-spontaneous at lower temperatures
Positive Negative Always non-spontaneous
Negative Positive Always spontaneous
Negative Negative Spontaneous at lower temperatures
Non-spontaneous at higher temperatures
∆G = ∆H - T∆S
Task: Use the equation to help yourself reason these through
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Another visual - MAKE YOUR OWN!
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Practice Questions
◎ Using data from the data booklet, calculate ΔGo for the
following reactions using both methods, and Substance ∆Hof kJ mol-1
comment on whether the reaction is spontaneous.
HCl(g) -92
Assume 298 K.
○ Note: in some cases you will first need to calculate Substance So J K-1 mol-1
ΔHo and ΔSo. SO2(g) 248
○ Extension: for non-spontaneous reactions, find the O2(g) 205
minimum temperature necessary to make them HCl(g) 187
spontaneous, and for spontaneous reactions, find Cl2(g) 223
the maximum temperature where they are
S(g) 32
non-spontaneous
C5H12(l) 58.5
1. S(s) + O2(g) → SO2(g) – see next slide for example
Substance ∆Gof kJ mol-1
SO2(g) -300
2. C5H12(l) → CH4(g) + 2C2H4(g)
3. CH4(g) + 3Cl2(g) → CHCl3(g) + 3HCl(g)
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1. S(s) + O2(g) → 🡪 SO2(g)
◎ Method 1:
○ ΔH = -297 kJ mol-1 This is in the data booklet as ΔHc for sulfur
○ ΔS = 248 – (32 + 205) = 11 J K-1 mol-1 Data is on previous slide
○ ΔG = ΔH - TΔS
= -297 – (298 x 11)/1000
-1
At what temperature
= -300 kJ mol does it become non
◎ Method 2: spontaneous?
∆G SO2(g)
S(s) + O2(g) - This reaction is always
∆G1 = 0 + 0 = 0 ∆G2 = -300 spontaneous, since ΔH is
S(s) + O2(g) negative and ΔS is positive.
∆Go = -0 + -300
= -300 kJ mol-1
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Negative therefore spontaneous at this temp
Summarising
◎ ΔG = ΔH - TΔS
◎ The mathematics means that:
○ Some reactions are spontaneous at all temperatures
○ Some reactions are only spontaneous above certain temperatures
○ Some reactions are only spontaneous below certain temperatures
◎ ΔS and ΔG can be calculated using:
○ Hess cycles
Or
○ ∑ (formation products - formation reactants) like ΔH
