Thermodynamics pt 1: Introduction to Spontaneity, Entropy, and Gibbs Free Energy SUGGESTED HW: Ch 23: 7, 11, 13, 17, 21

Intro to Thermodynamics Some things happen without influence, some things don’t. For example, decay just happens, without input. But creation requires work. Water flows downhill, but you need a pump to force water uphill. Iron exposed to air will rust (Fe 2 O 3 ). But rusted iron will not re-convert to Fe(s) and O 2. These are examples of irreversible processes. X

Spontaneity What determines the direction of a process? The first law of thermodynamics tells us that This means that if a reaction occurs, the total energy of the universe is unchanged. In this lecture, we address the word “if”. Why do some reactions occur, whereas others don’t? Let’s first begin by determining the criteria for a spontaneous process

Spontaneity A spontaneous process is any process that occurs without external influence. ALL SPONTANEOUS PROCESSES ARE IRREVERSIBLE Work must be done by the surroundings to return the system to the original state, but this leaves the surroundings permanently changed. HotCold Thermodynamics allows us to determine if a process will occur, and in which direction. Kinetics tells us how fast the reaction will go.

Spontaneity Spontaneous changes need not be fast. Ex. Diamonds spontaneously convert to graphite, but this process takes centuries. What dictates the tendency of a process to spontaneously occur? When this question was first addressed in the 1860’s, it was thought that the only criteria for spontaneity was that a reaction be exothermic.

Spontaneity Since exothermic processes are “energetically downhill” processes, it was a logical assertion. However, this was quickly proved to be incorrect. The dissolution of NaCl(s) in water is spontaneous, but endothermic Some spontaneous processes are temperature dependent. For example, ice spontaneously melts at any temperature greater than 0 o C.

Entropy What is the common pattern with all spontaneous change? Spontaneous changes lead to increases in disorder. Expansion of gases creates a randomized, less ordered system Liquid water is much less ordered than ice. Ice atoms are held in place, liquid atoms tumble around. Dissolving a salt in water yields ions that are free to move about randomly The cooling of a hot block in air results in energy transfer to surrounding air molecules, which increases their kinetic energy and leads to more random motion and collisions This disorder is called ENTROPY (S)

The more disordered a system, the larger its entropy. Entropy, denoted S, is a state function, so it depends only on the initial and final states, not the path taken. An increase in disorder represents a positive change in entropy (ΔS > 0), while increases in order are negative (ΔS < 0) Suppose a system undergoes a process in which it changes from an initial state (1) to a final state (2). The heat transferred during this process DOES depend on the path To relate ΔS to heat, we consider a reversible path between the states. Entropy

Reversible Processes Imagine we have a reversible process. In a reversible process, the direction of a process can be reversed by an infinitesimally small change in one variable (Attaining a reversible condition is theoretical) Ex. Water at exactly 0 o C. The tiniest change in pressure at constant temperature (isothermal) will cause the water to move either toward the solid or liquid phase. Because this pressure change is so small, no work is done, and thus, none is required to reverse the pressure change. Whenever a chemical system is in equilibrium, we can go reversibly between states without input of work or energy. H 2 O(s) H 2 O(L) 0 o C

Example: Entropy Change for “Reversible” Processes For an isothermal process, like a phase change: The subscript “rev” indicates that the transfer of heat is reversible, so the system is in equilibrium. The heat term in the numerator accounts for the proportionality between thermal transfer and disorder. The temperature term in the denominator accounts for the disorder that already exists in the system.

THE ENTROPY OF THE UNIVERSE IS CONTINUALLY INCREASING. Second Law of Thermodynamics For any irreversible process in which the system becomes more ordered, the increase in disorder of the surroundings must be greater in magnitude, and visa versa. The universe can NEVER become more ordered.

Considering the example of rust: ΔS sys is NEGATIVE. Why? Most combination reactions have negative entropy because you are reducing the number of free species. Here, we have taken 7 total moles of reactant and formed 2 moles of product Gases have much higher entropies than solids. Here, we have consumed a gas to form a solid. ΔS surr is POSITIVE because the reaction is highly exothermic. The thermal energy gained by the surrounding atmosphere causes a high degree of disorder in the surrounding gas molecules. The disorder to the surroundings caused by this process MUST be greater than the order obtained by the system.

Molecular Interpretation of Entropy When we have a process than reduces the total number of free species, or changes phase from gas to liquid/solid or liquid to solid, we limit the motion of the molecules (i.e. the number of ways they can release energy) There are three types of motion: translational, vibrational, rotational. The number of ways molecules can move are its degrees of freedom Translational (full movement) molecule moves from one place to another

Degrees of Freedom Vibrational motion only Vibrational motion, restricted rotational & translational motion Free motion Gases, being the least ordered, have the most ways of dissipating thermal energy. Hence, they have the highest entropy.

Determine the sign of ΔS sys A(g) + 2B(g) ---> AB 2 (s) H 2 O(s) ---> H 2 O (L) NaCl(s) ---> Na + (aq) + Cl - (aq) FeCl 2 (s) + H 2 (g) ---> Fe(s) + 2HCl(g) A(g) + 2B(g) ---> C(g) H 2 O (L) negative positive negative

Third Law of Thermodynamics All molecular motion stops at 0 o K (absolute zero). Therefore, S=0, and the molecules arrange themselves in perfect order. The plot below shows a heating curve of entropy. The sharp increases at phase boundaries is due to the added degrees of freedom

Calculations of Entropy Changes of Reactions Standard molar entropies, S o (J/mol K) are shown to the right. 1.Unlike enthalpies of formation, entropies are NOT zero for elemental forms of substances 2.Gases > Liquids > Solids 3.For the same phase, entropy increases with molar mass 4.For the same phase and same molar mass, entropy increases with the number of atoms in the molecule.

Examples Which would you expect to have the higher molar entropy? H 2 O(L) or H 2 O(g) CO 2 (g) or H 2 O(g) CO(g) or CO 2 (g) Zn(s) or Li(s) NaClO 4 (s) or He(g)

Example Calculate the standard entropy change: Make sure equation is balanced. Use stoichiometric coefficients and values from the table. products reactants

So What is the Criteria for Spontaneity? We have seen that spontaneous processes increase the entropy of the universe ΔH sys does not have to be negative, and ΔS sys does not have to be positive. This brings us back to the initial question: What is the criteria of a spontaneous process? Let’s use ΔH and ΔS concurrently to derive an expression

Math Time: Derivation of Gibbs Free Energy If the surroundings include “everything else”, then we can assert that for any process occurring in the system, the surroundings are large enough that their temperature and pressure are constant. Gibbs Free Energy

Sign of Gibbs Free Energy Dictates Direction of Reaction If ΔG is negative, the reaction is spontaneous in the forward direction If ΔG is zero, the reaction is at equilibrium If ΔG is positive, the reaction is spontaneous in the reverse direction

What is Gibbs Free Energy? As you would imagine, it is very difficult to directly calculate ΔS univ. However, the Gibbs Free Energy (-TΔS univ ) allows us to relate it to ΔH and ΔS of the system. Hence, by following the 2 nd law of thermodynamics, ΔG tells us about the spontaneity of a process Physically speaking, ΔG is the maximum useful work that can be done by a system on the surroundings at temperature T. In other words, all of the internal energy U of a system not accounted for by ΔG will be lost as heat. When ΔG is positive, this value represents the minimum work that must be done to the system to force the reaction to proceed.

Now We See That Spontaneity Depends on Enthalpy AND Entropy Dictates if a process is energetically favored Dictates if a process is entropically favored