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Gibbs free energy and spontaneity

How the second law of thermodynamics helps us determine whether a process will be spontaneous, and using changes in Gibbs free energy to predict whether a reaction will be spontaneous in the forward or reverse direction (or whether it is at equilibrium!). 

Key points

  • The second law of thermodynamics says that the entropy of the universe always increases for a spontaneous process: ΔSuniverse=ΔSsystem+ΔSsurroundings>0
  • At constant temperature and pressure, the change in Gibbs free energy is defined as ΔG=ΔHTΔS.
  • When ΔG is negative, a process will proceed spontaneously and is referred to as exergonic.
  • The spontaneity of a process can depend on the temperature.

Spontaneous processes

In chemistry, a spontaneous processes is one that occurs without the addition of external energy. A spontaneous process may take place quickly or slowly, because spontaneity is not related to kinetics or reaction rate. A classic example is the process of carbon in the form of a diamond turning into graphite, which can be written as the following reaction:
C(s,diamond)C(s,graphite)
On left, multiple shiny cut diamonds. On right, chunk of black graphitic carbon.
Ever heard the saying, "graphite is forever"? If we waited long enough, we would observe a diamond spontaneously turn into the more stable form of carbon, graphite. Picture from Wikipedia, CC BY-SA 3.0
This reaction takes so long that it is not detectable on the timescale of (ordinary) humans, hence the saying, "diamonds are forever." If we could wait long enough, we should be able to see carbon in the diamond form turn into the more stable but less shiny, graphite form.
Another thing to remember is that spontaneous processes can be exothermic or endothermic. That is another way of saying that spontaneity is not necessarily related to the enthalpy change of a process, ΔH.
How do we know if a process will occur spontaneously? The short but slightly complicated answer is that we can use the second law of thermodynamics. According to the second law of thermodynamics, any spontaneous process must increase the entropy in the universe. This can be expressed mathematically as follows:
ΔSuniverse=ΔSsystem+ΔSsurroundings>0        For a spontaneous process
Great! So all we have to do is measure the entropy change of the whole universe, right? Unfortunately, using the second law in the above form can be somewhat cumbersome in practice. After all, most of the time chemists are primarily interested in changes within our system, which might be a chemical reaction in a beaker. Do we really have to investigate the whole universe, too? (Not that chemists are lazy or anything, but how would we even do that?)
Luckily, chemists can get around having to determine the entropy change of the universe by defining and using a new thermodynamic quantity called Gibbs free energy.

Gibbs free energy and spontaneity

When a process occurs at constant temperature T and pressure P, we can rearrange the second law of thermodynamics and define a new quantity known as Gibbs free energy:
Gibbs free energy=G=HTS
where H is enthalpy, T is temperature (in kelvin, K), and S is the entropy. Gibbs free energy is represented using the symbol G and typically has units of kJmol-rxn.
When using Gibbs free energy to determine the spontaneity of a process, we are only concerned with changes in G, rather than its absolute value. The change in Gibbs free energy for a process is thus written as ΔG, which is the difference between Gfinal, the Gibbs free energy of the products, and Ginitial, the Gibbs free energy of the reactants.
ΔG=GfinalGinitial
For a process at constant T and constant P, we can rewrite the equation for Gibbs free energy in terms of changes in the enthalpy (ΔHsystem) and entropy (ΔSsystem) for our system:
ΔGsystem=ΔHsystemTΔSsystem
You might also see this reaction written without the subscripts specifying that the thermodynamic values are for the system (not the surroundings or the universe), but it is still understood that the values for ΔH and ΔS are for the system of interest. This equation is exciting because it allows us to determine the change in Gibbs free energy using the enthalpy change, ΔH, and the entropy change , ΔS, of the system. We can use the sign of ΔG to figure out whether a reaction is spontaneous in the forward direction, backward direction, or if the reaction is at equilibrium.
  • When ΔG<0, the process is exergonic and will proceed spontaneously in the forward direction to form more products.
  • When ΔG>0, the process is endergonic and not spontaneous in the forward direction. Instead, it will proceed spontaneously in the reverse direction to make more starting materials.
  • When ΔG=0, the system is in equilibrium and the concentrations of the products and reactants will remain constant.

Calculating change in Gibbs free energy

Although ΔG is temperature dependent, it's generally okay to assume that the ΔH and ΔS values are independent of temperature as long as the reaction does not involve a phase change. That means that if we know ΔH and ΔS, we can use those values to calculate ΔG at any temperature. We won't be talking in detail about how to calculate ΔH and ΔS in this article, but there are many methods to calculate those values including:
When the process occurs under standard conditions (all gases at 1bar pressure, all concentrations are 1M, and T=25C), we can also calculate ΔG using the standard free energy of formation, ΔfG.
Problem-solving tip: It is important to pay extra close attention to units when calculating ΔG from ΔH and ΔS! Although ΔH is usually given in kJmol-reaction, ΔS is most often reported in Jmol-reactionK. The difference is a factor of 1000!!

When is ΔG negative?

If we look at our equation in greater detail, we see that ΔGsystem depends on 3 values:

ΔGsystem=ΔHsystemTΔSsystem
  • the change in enthalpy ΔHsystem
  • the temperature T
  • the change in entropy ΔSsystem
Temperature in this equation always positive (or zero) because it has units of K. Therefore, the second term in our equation, TΔSsystem, will always have the same sign as ΔSsystem. We can make the following conclusions about when processes will have a negative ΔGsystem:
  • When the process is exothermic (ΔHsystem<0), and the entropy of the system increases (ΔSsystem>0), the sign of ΔGsystem is negative at all temperatures. Thus, the process is always spontaneous.
  • When the process is endothermic, ΔHsystem>0, and the entropy of the system decreases, ΔSsystem<0, the sign of ΔG is positive at all temperatures. Thus, the process is never spontaneous.
For other combinations of ΔHsystem and ΔSsystem, the spontaneity of a process depends on the temperature.
  • Exothermic reactions (ΔHsystem<0) that decrease the entropy of the system (ΔSsystem<0) are spontaneous at low temperatures.
  • Endothermic reactions (ΔHsystem>0) that increase the entropy of the system (ΔSsystem>0) are spontaneous at high temperatures.
Can you think of any reactions in your day-to-day life that are spontaneous at certain temperatures but not at others?

Example 1: Calculating ΔG for melting ice

Three melting ice cubes in a puddle of water on a mirrored surface.
At what temperatures (if any) is the melting of ice a spontaneous process? Photo of ice cubes from flickr, CC BY 2.0.
Let's consider an example that looks at the effect of temperature on the spontaneity of a process. The enthalpy of fusion and entropy of fusion for water have the following values:
ΔfusH=6.01kJmol-rxn
ΔfusS=22.0Jmol-rxnK
What is ΔG for the melting of ice at 20C?
The process we are considering is water changing phase from solid to liquid:
H2O(s)H2O(l)
For this problem, we can use the following equation to calculate ΔGrxn:
ΔG=ΔHTΔS
Luckily, we already know ΔH and ΔS for this process! We just need to check our units, which means making sure that entropy and enthalpy have the same energy units, and converting the temperature to Kelvin:
T=20C+273=293K
If we plug the values for ΔH, T, and ΔS into our equation, we get:
ΔG=ΔHTΔS=6.01kJmol-rxn(293K)(0.022kJmol-rxnK)=6.01kJmol-rxn6.45kJmol-rxn=0.44kJmol-rxn
Since ΔG is negative, we would predict that ice spontaneously melts at 20C. If you aren't convinced that result makes sense, you should go test it out!
Concept check: What is ΔG for the melting of ice at 10C?

Other applications for ΔG: A sneak preview

Being able to calculate ΔG can be enormously useful when we are trying to design experiments in lab! We will often want to know which direction a reaction will proceed at a particular temperature, especially if we are trying to make a particular product. Chances are we would strongly prefer the reaction to proceed in a particular direction (the direction that makes our product!), but it's hard to argue with a positive ΔG!
Thermodynamics is also connected to concepts in other areas of chemistry. For example:

Summary

  • The second law of thermodynamics says that the entropy of the universe always increases for a spontaneous process: ΔSuniverse=ΔSsystem+ΔSsurroundings>0
  • At constant temperature and pressure, the change in Gibbs free energy is defined as ΔG=ΔHTΔS.
  • When ΔG is negative, a process will proceed spontaneously and is referred to as exergonic.
  • Depending on the signs of ΔH and ΔS, the spontaneity of a process can change at different temperatures.

Try it!

For the following reaction, ΔHrxn=120kJmol-rxn and ΔSrxn=150Jmol-rxnK:
2NO(g)+O2(g)2NO2(g)
At what temperatures will this reaction be spontaneous?
Note: Remember that we can assume that the ΔH and ΔS values are approximately independent of temperature.
Choose 1 answer:

Want to join the conversation?

  • starky ultimate style avatar for user natureforever.care
    Well I got what the formula for gibbs free energy is. but what's the nature of this energy and why is it called 'free'? It does free work is what textbooks say but didn't get the intuitive feel.
    (22 votes)
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    • piceratops seed style avatar for user RogerP
      The word "free" is not a very good one! In fact, IUPAC recommend calling it Gibbs energy or the Gibbs function, although most chemists still refer to it as Gibbs free energy.

      Gibbs originally called it available energy and that is a good term because it is the energy associated with a chemical reaction that is available (or you could say free) to do work, assuming constant T and P.
      (27 votes)
  • aqualine ultimate style avatar for user Ben Alford
    Is there a difference between the notation ΔG and the notation ΔG˚, and if so, what is it?
    (10 votes)
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    • blobby green style avatar for user dmelby
      STP is not standard conditions. Standard conditions are 1.0 M solutions and gases at 1.0 atm. Standard conditions does not actually specify a temperature but almost all thermodynamic data is given at 25C (298K) so many people assume this temperature.
      (4 votes)
  • blobby green style avatar for user ila.engl
    Hey I´m stuck: The ∆G in a reaction is negative but the ∆H was positive and it is assumed that a change temperature doesn´ t significantly affect entropy and entalpy. What does this do to 1) spontanity 2) spontanity at high temp 3) value or sign of ∆S

    i read it 3 times now but i´m still insecure - :(
    (3 votes)
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    • orange juice squid orange style avatar for user awemond
      This looks like a homework question, so I'll give you some hints to get you on the riht path rather than answering directly.

      3) We know that ∆G = ∆H - T∆S. Solving for ∆S, we have:

      ∆S=(∆H-∆G)/T.

      We know (from the question) that ∆G is negative and that ∆H is positive. Temperature is always positive (in Kelvin). From these values, we can know for certain whether ∆S is positive or negative (hint: remember that we are subtracting ∆G!).

      1) Knowing the sign of ∆G is enough to say whether the reaction is spontaneous or not under these conditions. If ∆G is negative (from the question), is the reaction spontaneous or non-spontaneous?

      2) Let's use ∆G = ∆H - T∆S again. Since ∆H and ∆S don't change significantly with temperature (given in the question), we can assume that they keep the same signs and values: i.e. ∆H is still positive and ∆S is still whatever sign you figured out above. As T increases, the T∆S component gets bigger. T is always positive, so if ∆S is positive then a bigger T∆S will make ∆G more negative (since we subtract T∆S). If ∆S is negative, then the negative signs (from the subtraction and the sign of ∆S) will cancel out, and so as T∆S gets bigger, ∆G will get more positive.
      (12 votes)
  • blobby green style avatar for user Phoebe Hall
    In the subject heading, 'When is ΔG is negative?', is it a typo that it says
    'When the process is endothermic, ΔHsystem > 0, and the entropy of the system decreases, ΔSsystem>0, the sign of ΔG is positive at all temperatures. Thus, the process is never spontaneous' shouldn't the entropy be < 0? if there is a decrease in entropy?
    (4 votes)
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  • leaf green style avatar for user Jasgeet Singh
    The Entropy change is given by Enthalpy change divided by the Temperature. Then how can the entropy change for a reaction be positive if the enthalpy change is negative?
    (4 votes)
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  • male robot donald style avatar for user Kaavinnan Brothers
    Hi all, Sal sir said we would prefer the reaction to proceed in a particular direction (the direction that makes our product!), but it's hard to argue with a positive ΔG! ( located before summary at other applications of del G) .can anybody please explain?
    (2 votes)
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  • mr pants teal style avatar for user 1448169
    how do i see the sign of entropy when both reactant and product have the same phase
    (2 votes)
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    • piceratops ultimate style avatar for user Stephen R. Collier
      We have to look up the ΔS for the whole reaction in a table (or test the reaction ourselves... I'd rather look it up!). The value will be either positive or negative. If the reaction can result in a phase change then we might be lucky enough to find a list that has the reaction with reactant and products in the phases we need.

      Otherwise we could calculate the change in energy and the use the specific heat equations to see if the phase would change. The example above with melting ice looks a little different because the reaction was a phase change (ice to water) instead of the usual combining or splitting of molecules.
      (2 votes)
  • blobby green style avatar for user izzahsyamimi042
    can an exothermic reaction be a not spontaneous reaction ?
    (1 vote)
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  • duskpin seed style avatar for user estella.matveev
    Hi, could someone explain why exergonic reactions have a negative Gibbs energy value? I get it in terms of doing the calculations by looking at the graphs, but don't get it in terms of particles gaining or losing energy.
    (2 votes)
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    • leaf green style avatar for user Oliver McCann
      According to the laws of thermodynamics, ever spontaneous process will result in an increase in entropy and thus a loss in "usable" energy to do work. When an exergonic process occurs, some of the energy involved will no longer be usable to do work, indicated by the negative Gibbs energy.
      (1 vote)
  • duskpin ultimate style avatar for user anoushkabhat2016
    Is the reaction H2O(l) to H20(s) spontaneous or non spontaneous? The entropy, S, is positive when something goes from a solid to liquid, or liquid to gas, which is increasing in disorder. However, in this equation, water is going from a liquid to solid, so S is negative, and in the Gibbs free reaction equation, S must be positive for a reaction to be spontaneous. How do we determine, without any calculations, the spontaneity of the equation?
    (1 vote)
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    • duskpin ultimate style avatar for user Betty :)
      Using that grid from above, if it's an exothermic reaction (water is releasing heat into its surroundings in order to turn into ice), we know it's on the left column. The entropy of liquid water is higher than ice (water as a solid state)so therefore it is not always going to be spontaneous. Putting into the equation, ΔH<0 because it's exothermic, and ΔS<0 because entropy is decreased. Therefore, the reaction is only spontaneous at low temperatures (TΔS). If you think about its real-world application, it makes sense. Liquid water will turn into ice at low enough temperatures.
      (2 votes)