Chapter 17 Outline Chem 1062 1.

Energy Review introduced in Chap 6 of 1061 when the energy of a system was discussed the energy of a system, internal energy (E), is the sum of all of the kinetic and potential energies of the system as it is difficult (and not very useful) to measure the absolute energy of a system, we often look at changes in energy (E is a state function so it only depends on the initial and final state, not path) energy flowing into a system is considered positive energy flowing out of a system is considered negative during chemical reactions, much of the energy flow is as heat (q) or work (w) heat flow can be determined by temperature changes q = msT or q = CT work is typically electrical work (dealt with in the next chapter) or PV work most of the time, we are concerned with the heat of the reaction and we do our reactions under constant pressure conditions developed a new term called enthalpy (H) for these conditions where H = E +PV enthalpy and internal energy are the same unless gases are formed or consumed in the reaction (and even then it is a small change) we could calculate H for a reaction by calculating q, by adding appropriate reactions (Hesss Law), or by using standard enthalpies of formation in the equation H = np Hf (products) - nr Hf (reactants) a lot of what we did in 1061 was based on the first law of thermodynamics (energy cant be created or destroyed) there are two more laws we need to consider in this chapter, but first we need to introduce some new terminology

2. Entropy and Spontaneity a spontaneous change is one which occurs without continuous outside assistance all nonspontaneous changes occur at the expense of spontaneous ones the direction of a spontaneous change is often (but not always) in the direction of lower energy (they tend to be exothermic) more precisely, spontaneous processes tend to proceed from states of low probability to states of high probability eg: gases filling container in book eg: hot and cold molecules transferring heat

entropy (S) is a thermodynamical quantity that describes the number of equivalent ways that energy can be distributed in the system S = k lnW where k is Boltzmanns constant (R/NA = 1.38 x 10-23 J/K) the larger the value of S, the more energetically equivalent versions there are of the system and, therefore, the larger is its statistical probability because spontaneous events tend to disperse energy, entropy can be related to experimental heat and temperature measurements (as it is often impractical to count particle arrangements on a reaction scale) again, entropy is a state function (is independent of the path and only depends on temperature and pressure of current state) and thus we often describe changes in entropy S = Sfinal Sinitial or S = Sprod Sreact a positive value of S means that entropy (or the number of ways to disperse energy) has increased and thus that the event tends to be spontaneous it is often possible to predict the sign of S based on an increase in freedom of molecular motion 1. physical state S increases with increased movement of the particles Ssolid<Sliquid<<Sgas Ssoln < Saq 2. molecular complexity molecules with more atoms and bonds have a higher value of S due to more ways to vibrate (and thus disperse energy) 3. volume S increases with increasing volume for gases (more ways to distribute the kinetic energy since the molecules have more room to move about) 4. temperature S increases with increasing temperature (higher temperature leads to more movement of molecules which gives more ways to distribute the energy)

5. number of particles if all other things are equal (temp, volume, physical state), a reaction which increases the number of particles going from reactants to products will have an increase in entropy eg: Predict the sign of S for the following reactions. 2 NO2(g) N2O4(g) 2 NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g) C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(g) CaO(s) + SO2(g) CaSO3(s)

3. Second Law of Thermodynamics have spontaneity with enthalpy (tend to be exothermic) and with entropy (tends to increase) eg: burning CH4, melting ice, H2 + O2 also have a dependence on temperature eg: ice/H2O at 25 C and -25 C the second law can be used to relate enthalpy, entropy, and temperature to each other and figure out which is the dominate factor in a particular reaction according to the second law, whenever a spontaneous even occurs (in the universe), the total entropy of the universe (Suniv) increases the entropy of the universe is related to the system itself as well as the surroundings Suniv = Ssystem + Ssurroundings have said that can get Ssys from product reactants (will calculate in a bit) need to determine Ssurr entropy changes in the surroundings will be due to heat flowing in and out of the surroundings during a reaction (more heat flowing in/out gives more ways to disperse energy)

Ssurr qsys or -Hsys entropy changes are inversely proportional to temperature when looking at effects eg: rock in pond vs ocean Ssurr 1/T combining these, get an expression for Ssurr based on the reaction itself
Ssurr - H sys T

thus, the entropy of the universe in a chemical reaction is

Suniv Ssys H sys T

4. Third Law of Thermodynamics can calculate H for our reaction, but still need to be able to calculate S the third law allows us to actually measure what the absolute entropy of a substance is the third law states that the entropy of a perfectly crystalline substance at 0 K is zero (all motion ceases, so there is no way to distribute energy; W = 1) we can then work up from 0 K to determine the entropy of a substance at other temperatures (knowing how much heat has been added at what temperature) have tables of standard entropies (S) for compounds in the standard state (1 atm, 25 C, 1 M) unlike values of Hf, S of elements are NOT zero in the standard state (they are zero at 0 K); are still extensive properties can calculate the change in entropy (S) in the same way that the change in enthalpy was calculated S = np S (products) - nr S (reactants) eg: What is the change in entropy for the following reaction? CH3CH2OH(l) + O2(g) CH3COOH(l) + H2O(l) S (J/mol

Compound

CH3CH2OH(l) CH3COOH(l) H2O(l) O2(g)

K) 161 160 69.9 205

5. Free Energy and Spontaneity we can now talk about S and H for a reaction, but to determine if a reaction is spontaneous, we still need to look at the change in entropy for the universe as a whole would like to determine spontaneity just by using the system we previously have said that for a spontaneous event, the total entropy of the universe ( Suniv) increases (is positive) and that
Suniv H sys T Ssys

rearranging by multiplying by T gives the equation -T Suniv = Hsys - T Ssys this quantity, -T Stotal, was define by J. Willard Gibbs as the free energy of the system, Gsys, or the energy that need not be lost to surroundings as heat and therefore is free to be sued for work as G is related to H and S, it is also a state function and we usually are looking for changes in the free energy of the system notice that free energy is defined for the system, NOT for the universe or total since Suniv needed to be positive for a spontaneous event, Gsys (or -TSuniv) must be negative for a spontaneous event (or to favor the products of a reaction) can look at changes in free energy in the standard state ( G ) in the same way we looked at standard entropies and enthalpies o so, G = H - T S and can be calculated using values obtained for the enthalpy and entropy as before

o or G = n G f (products) - m G f (reactants) using tables of standard free energies of formation (free-energy change when 1 mol of substance is formed from its elements in their stablest states)

eg: What is G for the following reaction at 25 C? CH3CH2OH(l) + O2(g) Compound CH3CH2OH(l) CH3COOH(l) H2O(l) O2(g) CH3COOH(l) + H2O(l) S (J/mol K) 161 160 69.9 205

H f (kJ/mol) -277.6 -487.0 -285.8 0

in order for a reaction to be spontaneous, G must be a negative value overall the sign of the free energy will depend on the enthalpy and entropy of the system as well as the temperature at which the reaction is occurring

S is +

S is -

H is + H is G is at high G is always temps G is + at low temps G is always + G is + at high temps G is at low temps

the free energy of a reaction is also sometimes referred to as the maximum amount of work which can be obtained from a reaction (the free energy available to do work)

6. Free Energy and Equilibrium said that the free energy of a reaction is related to spontaneity (a value of G is spontaneous) equilibria is also related to spontaneity (a high value of K is likely to go forward) as both are related to spontaneity, they must be related to each other define a thermodynamic equilibrium constant (K) the same way as before except that it can combine concentrations and pressures when appropriate eg: What is the expression of K for the following reactions? N2O4(g) 2 NO2(g) Zn(s) + 2 H+(aq) Zn2+(aq) + H2(g)

in addition, both equilibria and free-energy change with temperature, so a way of relating the two to each other and to temperature would be good G = -RT lnK where R is the gas constant (8.314 J/mol K) and T is in K if one is known, the other can be calculated eg: What is the value of K for the reaction N2O4(g) 2 NO2(g) at 25 C? Compound N2O4 NO2 Gf (kJ/mol) at 25 C 97.82 51.3

eg: What is the value of K for the reaction Zn(s) + 2 H+(aq) Zn2+(aq) + H2(g) at 25 C? Compound Zn Gf (kJ/mol) at 25 C 0

Zn2+ H2 H+

-147.2 0 0

7. Free Energy under Non-Standard Conditions up to this point, all of our calculations have been under standard conditions (1 atm, 25 C, 1 M) the calculations that were done using G = -RT lnK were done to calculate the total amount of energy freed up as the reaction went from the very start until equilibrium was reached (in other words, until it stopped because it was all done) not all reactions are at standard conditions, so not all reactions will give that maximum amount of work calculated for standard conditions when we are not at standard conditions, we say that the reaction is not at equilibrium (K Q) and the reaction is still occurring another way of thinking about it is that we are looking at the amount of free energy available from some point in the middle of the reaction to the end so, we need to calculate the amount of free energy under the non-standard conditions (G) still available as the reaction is trying to proceed to equilibrium can express this as G = G + RT lnQ where G is the free energy at non-standard states (because it is still reacting) and Q has the same form as K using non-equilibrium amounts in this equation, the amount of free energy still available will be a portion of the total free energy of the reaction, the size of the proportion will be determined by how much Q is off from K notice that when we are at equilibrium, there will be no more energy given off, so G = 0 and the equation will rearrange to give G = -RT lnK as before to obtain G and K at temperatures other than 298 K, we need to approximate the value of G (or GT, as it is written in the equation below) using the equation relating free-energy, enthalpy, and entropy (assuming that enthalpy and entropy are essentially constant with respect to temperature) GT = H - TS and GT = -RT lnK (at other temperatures)

eg: Find G and K for the following reaction at 35 C. N2O4(g) 2 NO2(g) Compound Hf (kJ/mol) N2O4(g) 9.16 NO2 33.2 S (J/mol K) 304.3 239.9

can also calculate the temperature when a reaction becomes spontaneous (G = 0) eg: N2(g) + 3 H2(g) 2 NH3(g); H = -92.2 kJ; S = -198.7 J/K At what temperature will the reaction become spontaneous?

eg: For the N2O4(g) 2 NO2(g) reaction looked at before, what is the maximum temperature that must be obtained before the reaction becomes spontaneous?