Thermodynamics Page 1

Spontaneous and Nonspontaneous Processes
Although thermodynamics is an extensive discipline, the main question it addresses in
chemistry is whether or not a chemical process has a tendency to occur under given
conditions. If it does, we call it a spontaneous reaction/process.
So, why do we define spontaneity in terms of tendency?
Remember, a spontaneous process is not necessarily fast. For example, a new knife left
outside will eventually get rusty because it is a spontaneous process. The opposite will not
occur regardless of the time give.
Entropy Changes Associated with State Changes
On the basis of this is the third law of thermodynamics: the entropy of a perfect crystalline
substance is zero at the absolute zero of temperature.
The implication is that the entropy is the lowest in solids, and it keeps increasing in the order
of going to liquid and gas states. Remember this pattern, and the corresponding terms for each
process.
The changes are reversible and associated with heat of fusion, heat of vaporization, etc (qrev).
Under constant pressure, q = H, and it is correlated with the entropy change as shown below.

An example of a spontaneous reaction: Methane (natural gas) and oxygen have strong
tendency (highly exothermic) to react, so thermodynamically the reaction is spontaneous.

CH4(g) + 2 O2(g) CO2(g) + 2 H2O(l), H°rxn = -890 kJ

S is the entropy change of
Thankfully the gas does not explode in air just by itself. To initiate the reaction, a trigger the system measured in J/K,
such as ignition must be provided (recall activation energy). qrev is the heat exchanged
with the surroundings,
Kinetics focuses on the rate of T - temperature in Kelvin
the reaction. Remember, this Kinetics
How fast the
depends on the Ea barrier. Ea process occurs For the reverse process,
Energy

the sign of the enthalpy is

Thermodynamics is focused on changed: Hcond = - Hvap,
Will the
the initial and final stats. This Thermodynamics process occur? Hmelt = - Hfreez,
depends on the energy of these
states.
Reaction progress

Entropy
Most spontaneous processes are exothermic because they go downfall energetically. However,
enthalpy alone is not enough to explain why, for example, ice melts spontaneously above 0°C
even though the process is endothermic:
Example: Chloroform, CHCl3, is a common organic solvent once used as an anesthetic. a) Given
that the heat of vaporization of chloroform is 29.24 kJ/mol, calculate the entropy change, S of
the system when 1.00 mol of CHCl3 evaporates at its boiling point (61.2 °C). b) What is the
entropy of the gaseous chloroform at this temperature if the standard entropy of chloroform is
295.6 J/(mol K).

H2O(s) H2O(l) H° = 6.01 kJ/mol

The second factor affecting the spontaneity of a process is the entropy. It is very important in
thermodynamics, so let's start this study guide with it. What is entropy?
To find the entropy of chloroform in gas state, we need to add the S to its entropy at the
Entropy (S), a measure of disorder and randomness, is a quantity that explains the standard, liquid state:
spontaneity of a process. Low entropy means little disorder; high entropy means great
disorder. And, generally, a process associated with an increase in entropy is spontaneous. S (g) = S (l) + S = 295.6 J/(mol K) + 87.5 J/(mol K) = 383.1 J/(mol K)
gevorg@chemistrysteps.com
Copyright © 2022 Chemistry Steps
 Thermodynamics Page 2
Entropy Changes in Chemical Reactions Entropy Changes in the Surroundings
To predict the entropy change of a reaction, remember that it increases when (a) Physical state The change in entropy of the surroundings, Ssurr, is proportional to Hsys with an opposite
changes as: solid < liquid < gas (b) There are more products than reactants, (c) There are more sign: Ssurr - Hsys
products in gas state than reactants, (d) Dissolving solid. For example:

(a) H2O(s) H2O(l) H2O(g) S>0

Why are they proportional and why the minus sign?
Positive S since the freedom/randomness of H2O is increasing.

Exothermic Endothermic
(b) 3H2(g) + N2(g) 2NH3(g) S<0

Negative S since there are less (gas) products than reactants.

Ssurr
(c) 2SO3(g) 2SO2(g) + O2(g) S>0 exo endo
- Hsys + Hsys
Positive S since there are more products than reactants.
Ssurr
(d) Ca3(PO4)2(s) 3Ca2+(aq) + 2PO43-(aq) S>0

Positive S since dissolution of the solid calcium phosphate will increase the randomness The heat transferred to the surroundings
of Ca2+ and PO43- ions. increases the entropy of the surroundings
as the enhances motion of the molecular
The pattern is that entropy increases with randomness/freedom/positional probability.
motions are enhanced.
The heat absorbed from the
surroundings by the system decreases
the entropy of the surroundings
because molecular motion decreases.

Standard Entropy Change ( So)

Example: Given the H°rxn, calculate the Ssurr at 298 K when H°rxn = -2560 kJ.
Entropy change can be calculated based on the standard entropies (S°) - the absolute entropy
Entropy is usually given in J/K mol, so first convert the units of H°rxn
of a substance at 1 atm and 25°C.

So, unlike Hof and Gof for elements is not zero at 25 °C. H°rxn = -2560 kJ = -2.56 x 106 J/mol

We know how to calculate Horxn (check the thermochemistry guide) and because entropy is
also a state function, you can determine Sorxn by:

How are Ssys and Ssurr correlated?

Suniv = Ssys + Ssurr Ssys

Example: Given the values of So, calculate S°rxn for the following reaction at 25°C:
Suniv
Overall, whether a process is spontaneous
2H2S(g) + 3O2(g) 2SO2(g) + 2H2O(l)
or not depends on the magnitudes of Ssys
S° (J/K): for H2S(g) = 205.8, for O2(g) = 205.2, for SO2(g) = 248.2, for H2O(l) = 70 and Ssurr which together make the Ssys.
S°rxn = [2 x S° (H2O) + 2 x S° (SO2)] – [2 x S° (H2S) + 3 x S°(O2)] Ssurr
S°rxn = [2 x 70 J/K + 2 x 248.2 J/K] – [2 x 205.8 J/K + 3 x 205.2 J/K] = -390.8 J/K Remember, according to the second law of thermodynamics, for any spontaneous process,
the entropy of the universe increases ( Suniv > 0).
gevorg@chemistrysteps.com
Copyright © 2022 Chemistry Steps
 Thermodynamics Page 3
Gibbs Free Energy
We mentioned that according to the second law of thermodynamics, for any spontaneous For Example: Given the values H°rxn = -18,000 J , and S°rxn = -70 J/K, calculate the
process, the entropy of the universe increases ( Suniv > 0). G°rxn at 25 oC. (a) Is the process spontaneous? (b) If not, at what temperature will it
So, how do we measure the entropy change of the universe? become spontaneous?
It is beyond our capabilities to measure the entropy change of the universe, however, we can (a) Gorxn = Horxn - T Sorxn = -18,000 J - (25 + 273) (-70 J/K) = 2,860 J
use the formula from the previous page, linking Ssurr to the system:
Gorxn > 0, therefore, the process is nonspontaneous at 25 oC.

(b) To find the temperature at which the reaction becomes spontaneous, first, set G = 0
which corresponds to the equilibrium and determine the corresponding temperature.
Plugging this expression in the equation for Suniv, and multiplying everything by -T, we get:

-T Suniv = Hsys - T Ssys 18,000

G = H – T S, 0 = H – T S = = 257 K
70
The term, (-T Suniv) is called Gibbs free energy ( G), and it is a comprehensive quantity to
assess the spontaneity of a process because it takes into account the enthalpy, entropy, and Next, identify the favorable term that makes G negative. In this case, H is the
the temperature. favorable term because it is negative and decreases the G.
o o
G = H -T S o Because the entropy is negative, T Sorxn is positive, so we need to make the T Sorxn a less
significant contributor by decreasing the temperature. It means the process will become
So, Go is calculated by the parameters of the system, but it includes the Suniv just with the
spontaneous below 257 K.
opposite sign.
If the Horxn and Sorxn are not given in the problem, you need to calculate them first,
Negative G (exergonic) means a spontaneous, while positive G (endergonic) means a using the data in appendix and then plug the values in the Gibbs free energy equation.
nonspontaneous process. When G = 0, the system is at equilibrium.
Strictly speaking, the Gibbs free energy should only be used for reactions carried out at 25 oC
Negative H and a larger T S are favorable for making a process spontaneous:
since Hof and So are given for that temperature. However, it is used for higher temperatures
Smaller H, smaller G: H G too. More about this on page 4.

Larger T S , smaller G (because of the negative sign): T S G Another example: Is the reaction with following parameters spontaneous at 25 oC? If not, at
what temperatures will it be spontaneous?
Correlating G with H and S
H = +25.0 kJ, S = +40.0 J/K
• If H is negative and S is positive, G is always negative.
• If H is positive and S is negative, G is always positive. G = H - T S = +25.0 kJ - 298 K x 0.0400 kJ/K = +13.08 kJ
If both H and S are positive, then G will be negative only when the T S > H. G > 0, so the reaction is nonspontaneous at 25 oC.
Increasing the temperature will favor spontaneity.
To find the temperature at which the reaction becomes spontaneous, first, set G = 0 which
If both H and S are negative, then G will be negative only when the T S < H.
corresponds to the equilibrium and determine the corresponding temperature.
Decreasing the temperature will favor spontaneity.

G= H-T S G = H – T S, 0 = H – T S

H - + + - only when the T S > H (high temp.)

If Next, identify the favorable term that makes G negative. In this case, S is the favorable
S + - + -
only when the T S < H (low temp.) term because it is positive and negative sign decreases the G. Therefore, the process will
Then G - + - -
depends become spontaneous when the temperature becomes higher than 625 K.
on T S gevorg@chemistrysteps.com
Copyright © 2022 Chemistry Steps
 Thermodynamics Page 4
o
Standard Free-Energy Changes ( G ) G of a Reaction under Nonstandard Conditions
The standard free-energy of reaction ( G°rxn) is the free-energy change for a reaction So far, all the processes and reactions we discussed were for standard conditions ( Go).
when it occurs under standard-state conditions. The free energy change for a process under nonstandard conditions is calculated by:
The standard free-energy change for a reaction can be calculated by this equation:
G = Go + RT ln Q
np - coefficients of products
nr - coefficients of reactants Q is the reaction quotient expressed in partial pressures or concentrations.
Under standard conditions, G = Go because Q = 1 (all gases are at 1 atm, all
Gof is the Standard Free-Energy of Formation; the free-energy change when 1 mole of concentrations 1 M), and thus ln Q = 0.
the substance is formed from its constituent elements in their standard states.
This equation explains why water evaporates at room temperature while Go > 0.
Check the thermochemistry guide for the conventions for Standard States:
H2O(l) H2O(g) Go = +8.59 kJ/mol
For a pure element (Na, Se, O2) in its standard state, Gof = 0.
The trick is that under ordinary conditions, the partial pressure of water vapor is
Example: Given the values of Gof, calculate G°rxn for the following reaction at 25°C:
much less than 1 atm; it is about 0.0313 atm.
2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(l) For the evaporation process, Q = PH2O, so for G, we have:

Gf° (kJ/mol): for C2H6(g) = -46.2, for O2(g) = 0, for CO2(g) = -394.4, for H2O(l) = -237.2 kJ J
G = Go + RT ln Q = 8.59 + ln
mol mol K
G°rxn = [6 x Gf° (H2O) + 4 x Gf° (CO2)] – [2 x Gf° (C2H6) + 7 x Gf° (O2)]
G°rxn = [6 x (-237.2 kJ) + 4 x (-394.4)] – [2 x (-32.89 kJ) + 7 x 0] = -2935 kJ/mol The process is at equilibrium, G = 0 meaning it is not favored at any direction.
Increasing the temperature will favor the evaporation.

G°rxn and Hess’s Law

Because free energy (G) is a state function, the Hess’s Law applies to Grxn as well:
When Solving Problems:
C Remember to convert the units of pressure to atm before using in the quotient.
2A + B C G° = +50 kJ G° +50
Remember to match the units of entropy with those of enthalpy and free energy.
+ 2A + B G°
C 2D G° = -80 kJ -80 Convert both to J or kJ.
G° -30
2A + B 2D G° = -30 kJ D Remember, you can only use he G°f from the appendix if the reaction is
Go = +50 - 80 = -30
carried out at 25 oC (298 K). If it is not, then G° is calculated using the equation
Example: Use the given data for reactions 1 and 2 below to calculate Go for reaction A: G° = H° – T S°.
(A) Fe2O3(s) + 3 CO( g) 2 Fe(s) + 3 CO2( g) So, this equation does not work for higher temperatures:

1) 2 Fe(s) + 3/2 O2(g) Fe2O3(s), Go = -742 kJ G°rxn = n G°f(products) – n G°f(reactants)

You may ask how come we can use the tabulated values of H°f and S° but not G°f.
2) 3 CO(g) + 3/2 O2(g) 3 CO2(g), Go = -771 kJ
The reason is that although the enthalpies and entropies are affected by temperature,
We need to reverse the first equation to make Fe a product: the difference between their values is very little compared to the temperature change.
1a) Fe2O3(s) 2 Fe(s) + 3/2 O2(g), Go = + 742 kJ As a result, the values of H° and S° do not change much with temperature.
+ However, G° is more sensitive to temperature which we can see by the presence
2) 3 CO(g) + 3/2 O2(g) 3 CO2(g), Go = -771 kJ of T in the equation G° = H° – T S°.
o
Fe2O3(s) + 3 CO( g) 2 Fe(s) + 3 CO2( g), G rxn = + 742 kJ - 771 kJ = -29 kJ
gevorg@chemistrysteps.com
Copyright © 2022 Chemistry Steps
 Thermodynamics Page 5
Example: Calculate G for the reaction at 298 K and the following partial pressures: Example: Calculate the equilibrium constant at (a) 25 °C and (b) 495 K for the following
reaction.
4HCl(g) + O2(g) 2Cl2(g) + 2H2O(g) 2SO3(g) 2SO2(g) + O2(g)

P (HCl) = 50.0 mmHg, P (O2) = 35.0 mmHg, P (H2O) = 125 mmHg, P(Cl2) = 182 mmHg (a) Calculate first the Go and then use it in the equation Go = –RT ln K to determine
the equilibrium constant.
The reaction is at nonstandard conditions, therefore, we need to use the following equation:
Go = [2 Gof(SO2(g)) + Gof(O2(g))] – [2 Gof (SO3(g))]
G = G° + RT ln Q
Go = [2 (-300) + 0] – 2 x (-371)] = 142 kJ
Using the data from the appendix in a textbook, calculate first the G°.
Go = –RT ln K
G° = [2 G°f (Cl2(g)) + 2 G°f (H2O(g))] – [4 G°f (HCl(g)) + G°f (O2(g))]
You can either calculate the exponent term separately or use the numbers in this equation.
G° = [2 x 0 + 2 x (-229)] – [4 x (-95) + 0] = -78 kJ

Next, convert the units of pressure to atm (1 atm = 760 mmHg) and use them in the
expression of Q:

(b) For higher temperatures, we use the Gibbs free energy equation, assuming the
enthalpies and entropies do not change much with temperature.

And now, we can use the numbers in the equation for G° at nonstandard conditions: H° = [2 (-297) + 0] – 2 x (-396)] = 198 kJ S° = [2 (248) + 205] – 2 x (257)] = 187 J/K

G° = H° – T S° = 198 kJ – 495 K x 0.187 kJ/K = 105.5 kJ

Relationship between Go and Equilibrium Constant K

Because at equilibrium, G = 0 and Q = K, we can write that = Go + RT ln K. Therefore,
o
G = -RT ln K
where K is the equilibrium constant (KP for gases and Kc for reactions in solution).
Based on this relationship, we can determine spontaneity at standard conditions:
Although the reaction is nonspontaneous at both conditions, increasing the temperature
has increased the equilibrium constant as well. This is expected for an endothermic
reaction (recall the Le Chateliers principle).
The Temperature Dependence of K
Combining the two equations for Gorxn, a new one is obtained that shows how the
equilibrium constant depends on temperature:

• When K < 1, ln K is negative and Gorxn > 0. Reaction is not spontaneous.

Gorxn = -RT ln K Gorxn = Horxn - T Sorxn -RT ln K = Horxn - T Sorxn
• When K > 1, ln K is negative and Gorxn < 0. Reaction is spontaneous.
• When K = 1, ln K = 0, Gorxn = 0. The reaction is at equilibrium. Dividing both sides by the RT, we get an equation in the form a straight line:
Notice that this is consistent with what we learn in the equilibrium chapter. Spontaneous
means the products are favored and nonspontaneous means reactants are favored. also
This equation is very important as it links two parameters indicating if the reaction is favored
under given conditions. y = mx + b
gevorg@chemistrysteps.com
Copyright © 2022 Chemistry Steps