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1 BIOC220 Chemical Thermodynamics (Chapter 19, Chemistry The Central Science, Brown et al.

) (1) How fast is the reaction? (depends on energy barrier and temperature) The Arrhenius equation: k = Aexp(Ea/RT) A : frequency factor for productive collision Ea : Activation energy (minimum energy required to initiate a chemical reaction) T : temperature k increases as T increases (approx. doubles for each 10oC increase) as Ea decreases (The lower energy barrier to overcome, the faster a reaction proceeds) (2) How far does the reaction proceed? (till equilibrium reaches when the opposing reactions occur at equal rates.) (3) Then, what is the connection between energy and the extent of a reaction? In which direction a reaction will proceed spontaneously? To what extent? [1] The First Law of Thermodynamics (p.170) E: Internal energy of a system: the sum of all the kinetic and potential energies of all its components. Energy transfer between systems and surroundings in two general ways, as work or heat E = q + w --- E : change in internal energy of a system q : heat added to a system w : work done on a system E > 0, when heat is added to the system (q > 0, endothermic), or work is done on the system (w > 0).
A system loses its internal energy (E < 0) by losing heat to the surroundings (q < 0, exothermic) or doing work on the surroundings (w < 0).

Many chemical reactions occur at constant pressure (P). Can we have a thermodynamic variable that makes it easier to measure energy change (E) at constant P? Often, the only kind of work produced by chemical changes is pressure-volume work, and at constant P, w = PV (negative as the system does work on the surroundings, losing energy) --- Enthalpy (H) = E + PV : The sum of internal energy plus the product of the pressure and volume, or : Heat flow in processes occurring at constant P when there is only P-V work. H = E + (PV) H = E + PV (at constant P, P = 0) ----

2 Substituting E in with and PV in with , H = E + PV = (qp + w) w = qp ------ Therefore, H is equal to the heat gained (lost) at constant P (qp). And, importantly, qp (H) is something that can be measured or calculated. Many chemical changes of interests occur at constant P. These make H more useful than E. Further, for most reactions H and E are similar anyways because PV is small. H > 0 when the system gains heat through an endothermic process, while H < 0 when the system loses heat through an exothermic process. In conclusion, H is a special case of heat transfer (qp) when only P-V work is involved at constant P. [2] Spontaneous Process (p.802) For discussion of entropy, a different textbook (Chemistry by Silberberg) was also consulted, which, I found, was easier to follow. From our experience, obvious are: There are spontaneous processes: brick falling, gas expanding, rusting, a chemical reaction proceeding toward equilibrium, etc.... Direction of spontaneity depends on T and P. Ice melting at T > 0, water freezing at T < 0, etc... There are fast (gas expanding) and slow (rusting) spontaneous processes. Is there a thermodynamic quantity that tells us about the direction of spontaneity of a process?? A criterion to predict the direction of a spontaneous change? How about H? All exothermic (H > 0) processes are spontaneous? No. Although the majority of spontaneous processes are exothermic, there are spontaneous endothermic ones. Ice melting at room temperature (endothermic, H < 0) is spontaneous, so is water vaporizing and salt melting, etc. What are the common features of these endothermic spontaneous processes? The component particles have more freedom of motion after the change occurs, or, in other words, their energy of motion becomes more dispersed, during phase change: solid liquid gas dissolving of salt: crystalline solid + liquid ions in solution chemical change: crystalline solids gases + ions in solution

Boltzmanns statistical interpretation of Entropy Recall quantized energy levels of atoms and molecules. Electronic energy levels of an atom or molecules, and Kinetic (vibrational, rotational, transitional) energies of molecules are all quantized. Each quantized state of the system is called a microstate. Every microstate has the same total energy at a given set of conditions, and each microstate is equally possible for the system. Entropy (S) of a system is related to the number of microstates (W) as: S = k ln W k : Boltzmanns constant (1.38 1023 J/K) = R/NA (gas constant/Avogadros number) W : the number of microstates associated with a particular macroscopic state Since W is dimensionless, S has units of J/K (energy/temperature). Therefore, A system with fewer microstates (smaller W) among which to spread its energy has lower S. A system with more microstates (larger W) among which to spread its energy has higher S. Ludwig Eduard Boltzmann (18441906) derived this equation in 1877 without any knowledge of quantum mechanics and the idea of quantinization. In fact, he wrote that his mathematical treatment of kinetic theory of gases is not concerned with a real physical problem. Quantifying S (1) A statistical approach Consider a simple case of 1 mol of an ideal gas, say Ne, expanding from 10 L to 20 L at 298 K.
1 mol Ne (initial: 10 L at 298 K) 1 mol Ne (final: 20 L at 298 K)

We can imagine two 10 L flasks connected by a stopcock. At the initial state, 1 mol of Ne is confined in one flask, and another flask is empty. We know from experience, the gas will expand to fill spontaneously, but why? Lets start with one Ne atom. One atom has some number of microstates (W) possible for it in one flask, and the same number possible in another flask. Opening the stopcock increases the volume, which increases the number of possible translational energy levels. As a result, the system has 21 as many microstates possible when the atom moves through both flasks. With two atoms moving through two flasks, there are 22 times as many microstates as when two atoms are confined initially in one flask, and so on... till 2NA times as many microstates possible for 1 mol of Ne atoms. Wfinal/Winitial = 2NA Ssystem = Sfinal Sinitial = k ln Wfinal k ln Wfinal = k ln (Wfinal/Winitial) = k ln (2NA) If we plug in the constants, for 1 mol, Ssystem = 5.76 J/K

Entropy and the Second Law of Thermodynamics Some spontaneous changes (water freezing) end up with lower entropy (liquid to solid). If we consider changes in both the system and its surroundings, we find that all real processes occur spontaneously in the direction that increases the entropy of the universe (system plus surroundings). the 2nd law of thermodynamics Suniverse = Ssystem + Ssurr > 0 (1) C6H12O6(s) + 6O2(g) 6CO2(g) + 6H2O(g) + heat Ssystem > 0 (solid to gas) Ssurr > 0 (heat produced) Therefore, Suniverse > 0, spontaneous. (2) CaO(s) + CO2(g) CaCO3(s) + heat Ssystem < 0 (gas to solid) Ssurr >> 0 (heat produced) Therefore, Suniverse > 0, spontaneous. (3) heat + Ba(OH)28H2O(s) + 2NH4NO3(s) Ba2+(aq) + 2NO3(aq) + 2NH3(aq) + 10H2O(l) Ssystem >> 0 (3 mol give 15 mol) Ssurr < 0 (heat absorbed from the surroundings) Therefore, Suniverse > 0, spontaneous. Now, how to measure Ssurr? The essential role of the surroundings during chemical changes is to either add heat to the system or remove heat from it. In essence, the surroundings function as an enormous heat source, one so large that its T remains constant, although its S changes through the loss or gain of heat. The surroundings participate in the two possible types of enthalpy changes as follows: (1) Exothermic change: Heat loss by the system is gained by the surroundings. This heat gain increases the freedom of motion of particles in the surroundings, hence Ssurr > 0. qsys < 0, qsurr > 0, and Ssurr > 0 (2) Endothermic change: Heat gained by the system is lost by the surroundings. Likely, qsys > 0, qsurr < 0, and Ssurr < 0 The temperature of the surroundings at which the heat is transferred also affects Ssurr. If the same amounts of heat is transferred to the surroundings of two different temperature, its effect will be larger at lower T, since at lower T, there is relatively little energy dispersed from the beginning (It is like depositing $10 to a checking account that has $10 in it. A huge effect. The same transaction to an account with $1000, little effect.) Ssurr is directly related to an opposite change in the heat of the system and inversely related to the temperature at which the heat is transferred. Hence, qsys Ssurr = T Recall qp = H at constant P (see above eq. ), so Hsys

5 Ssurr = T By making two separate measurements, Ssystem and Ssurr, we can predict whether a reaction will be spontaneous. Now, can we have one criterion for spontaneity that applies only to system? [3] Entropy, Free Energy, and Work From the 2nd law of thermodynamics, Suniverse = Ssystem + Ssurr At constant P, Ssurr = T Combing these two gives Suniverse = Ssystem (Hsys/T) Multiplying both sides by T gives TSuniverse = Hsys TSsystem Now, let us introduce a new term, free energy (G) that combines the systems enthalpy and entropy so that G = H TS. The Gibbs free energy change of the system (Gsys) at constant T and P: Gsys = Hsys TSsys = TSuniverse The 2nd Law of Thermodynamics dictates Suniverse > 0 for a spontaneous process Suniverse < 0 for a nonspontaneous process Suniverse = 0 for a process at equilibrium Since T is always positive, TSuniverse > 0 for a spontaneous process. It follows that Gsys < 0 for a spontaneous process (For a spontaneous process at constant T and P, the free energy of the system always decreases.) Gsys > 0 for a nonspontaneous process Gsys = 0 for a process at equilibrium Finally, we have a single criterion for spontaneity, G, whose sign tells if a reaction is spontaneous. Notes: If a process is nonspontaneous in one direction (G > 0), it is spontaneous in the opposite direction (G < 0). The sign and magnitude of G tells us nothing about its rate. A spontaneous reaction with a large ve G can proceed extremely slowly. Hsys

[4] Standard Free Energy Change ( G0) Like H, S, and T, G is also a state function. This allows us to focus on the free energy change (G), no matter how the change is brought about. State function In thermodynamics, a state function is any property of a system that depends only
on the current state of the system, not on the way in which the system got to that state.

To compare G values of different reactions, we calculate the standard free energy change ( G0), which occurs when all components of the system are in their standard states. G0sys = H0sys TS0sys As well, G0rxn can be calculated with values for the standard free energy of formation ( G0f) of the components. G0f : the free energy change that occurs when 1 mol of compound is made from its elements, with all components in their standard states. Because free energy is a state function, we can combine G0f values of reactants and products to calculate G0rxn no matter how the reaction takes place: G0rxn = [sum of G0f(products)] [sum of G0f(reactants)] [5] G and the Work a System Can Do The free energy change (G) is a measure of the spontaneity of a process and of the maximum useful work (non-expansion work, w) available from the system as the process takes place. At constant T : dG = dH TdS (Here, we use d instead of to denote infinitesimal changes to deal with reversible processes.) Since dH = dE + PdV (see above Eq. ), dG = dE + PdV TdS dE = dw + dq (Eq. ). Hence, dG = dw + dq + PdV TdS The work done on the system consists of expansion work, PexdV, and non-expansion work, dw. Therefore, dG = PexdV + dw + dq + PdV TdS at constant P and T. Now we specialize to a reversible process, then for expansion work to be reversible, we need to match P and Pex, in which case PexdV + PdV = 0. As well, because the transfer of energy as heat is also reversible, we can replace dq by TdS. qsys qrev (Recall Ssurr = and Ssystem = ) T T Then, we are left with

7 At constant T and P, for a reversible process: dG = dwrev Since this relation holds for each infinitesimal step between the specified initial and final states, it applies to the overall change too. Hence, G = wmax (the amount of energy free for work under the given conditions) In any real process, work is performed irreversibly in a finite number of steps, we can never obtain the maximum work. The free energy not used for work is lost to the surroundings as heat. (Think of a car engine that gives off unharnessed energy as heat.) [6] Coupling of Reactions to Drive a Nonspontaneous (Unfavorable) Change In multistep reactions, one step may supply enough free energy for the other to occur. (Combustion of gasoline in a car engine supplies enough free energy to move a car.) Examples in class handout or any Chemistry textbooks. [7] Free Energy, Equilibrium, and Reaction Direction G is not the only one that tells us about the direction of a chemical reaction. One can also predict reaction direction by comparing the values of the reaction quotient (Q) and the equilibrium constant (K). Recall that If Q < K (Q/K < 1), the reaction goes forward as written. If Q > K (Q/K > 1), the reaction goes reverse as written. If Q = K (Q/K = 1), the reaction has reached equilibrium. No net reaction in either direction. Similarly, If Q/K < 1, then ln Q/K < 0, the reaction goes forward as written (G < 0). If Q/K > 1, then ln Q/K > 0, the reaction goes reverse as written (G > 0). If Q/K = 1, then ln Q/K = 0, at equilibrium (G = 0). Note that the signs of G and ln Q/K are identical for a given reaction directions. In fact, G = RT ln Q/K = RT ln Q RT ln K --- At standard state conditions where all concentrations are 1 M, G = G0 and Q = 1. Thus, G0 = RT ln K ----- 0 Now one can calculate G of a reaction from its equilibrium constant, K, or vice versa. As the relationship is logarithmic, a small change in G0 brings about a large effect in K. G0 = 10 kJ K = 2 102 G0 = 50 kJ K = 2 109 From Eq. and , G = RT ln Q/K = RT ln Q RT ln K = RT ln Q + G0 G = G0 + RT ln Q -----

8 (I will not derive Eq. here, but it has something to do with the free energy change with pressure (dG = VdP) and the P-V relationship of ideal gas, PV = nRT. For more details, refer to any advanced thermodynamics textbooks.)