17.2 Chemical Thermodynamics
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1 17.2 Chemical Thermodynamics Dr. Fred Omega Garces Chemistry 201 Miramar College Chaotic Spontaneity 1 Chemical Thermodynamics: Chaos
2 Thermodynamics Vs. Kinetics Chemical Thermodynamics - Study of Chemical reaction energetics i.e., CH 4 + 2O 2 CO 2 + 2H 2 O + E Thermodynamics Domain (State) Kinetics Domain (Path) CH 4 + O 2 Initial CO 2 + H 2 O Final Understanding a chemical reaction and its energetic properties lead to the spontaneity prediction of the reaction. 2 Chemical Thermodynamics: Chaos
3 Spontaneous Process Example of common Spontaneous process: Aging Objects falling Time sun rise Ink mixing Chem. Exams If a process is spontaneous in one direction, then under the same conditions the reverse process is nonspontaneous. i.e., We do not grow young, gas does not contract, H 2 O does not freeze at room temperature, time does not go backwards and exams are not canceled. Note under different conditions however, the reverse process can occur. i.e., Liquid freezes to solid at 0 C. 3 Chemical Thermodynamics: Chaos
4 History of Time - S. Hawkins Begs the Question- Under different conditions, does this mean we can indeed grow young? Stephen Hawkins - seminar at UCSB. Since the Big Bang, the Universe has been expanding. Ultimately we will reach the Big Crunch. When this occurs the universe will contract and time will turn back... we will remember tomorrow (the future) and objects will self-assemble spontaneously. We will rise from our grave and end in the wombs of our mother. The sun will rise from the west and set to the East. This won t happen because of the singularity Theorem. According to this theory, this point in space-time, the curvature tensor becomes infinite and we have an undefined term, i.e., dividing by zero (undefined). 4 Chemical Thermodynamics: Chaos
5 History of Time 5 Chemical Thermodynamics: Chaos
6 Spontaneity Rate Note that spontaneity has nothing to do with how fast process occurs. Spontaneity addresses whether the reaction does occur or does not occur. Thermodynamics provides information on conditions which does favor spontaneity. NaOH (s) E (release) E (absorb) NH 4 Cl ( aq) Energy NaOH ( aq) Energy NH 4 Cl ( s) Spontaneous because it is a downhill process. Spontaneous, but this is an up-hill process. Why? 6 Chemical Thermodynamics: Chaos
7 Enthalpy alone is not the answer Enthalpy by itself does not predict spontaneity... disorder plays a major role. 2nd Law of Thermodynamics When a system becomes more chaotic (more disordered) it is said to be at a state of higher entropy. Another factor influencing spontaneity is an increase of entropy (S) of the universe. Entropy - viewed as a measure of randomness or disorder. Ink dispersing, objects falling, your room becomes more disordered with time. 7 Chemical Thermodynamics: Chaos
8 Entropy Entropy is a measure of disorder A thermodynamic state function that increases with the number of energetically equivalent ways to arrange the components of a system to achieve a particular state. S = k ln W K = R / Nav = 1.38e -23 J/K, W = microstates 8 Chemical Thermodynamics: Chaos
9 The State of Things to Come Your room is a MESS It is a natural law that your room ALWAYS gets trashed 9 Chemical Thermodynamics: Chaos
10 Entropy - Why fight it? Entropy describes the number of arrangements (position/energy levels) that are available to a system.... what this means is that the likely events are those in which there is the highest probability of existing. i.e., Deal out 5 cards, what is the probability of a royal flush? Royal flush - 4 hands out of 1,302,544 Other hands - 1,302,540 out of 1,302,544 There is a greater probability of getting nothing than getting something. Nature prefers to take this path (of highest occurrence) Nature prefers you get nothing. 10 Chemical Thermodynamics: Chaos
11 Entropy and Microstates Chemical system can be described in similar logic. Why do gas mix? A system may take on a number of micro-states. Consider a 4-gas particle Relative probability of arrangements: 11 Chemical Thermodynamics: Chaos
12 Entropy and Microstates Chemical system can be described in similar logic. Why do gas mix? A system may take on a number of micro-states. Consider a 4-gas particle Relative probability of arrangements: 1: 4: 6 there is a greater probability of occurrence for mixing the particles. 13 Chemical Thermodynamics: Chaos
13 Entropy and Microstates (2) For a large number of gas molecules, there is a hugh number of micro-states in which equal number of molecules are in both end of the flask. On the other hand, the opposite process (gas molecules at only one end) although not impossible - it is highly improbable. Entropy states that any one of these micro-states are possible (or has some probability of occurrence). More States [ Larger Entropy (more likely event) 14 Chemical Thermodynamics: Chaos
14 Relative Entropy Entropy is a measure of disorder: In a phase change: Solid Liquid Gas Highly ordered Less ordered Very disordered temp. solids g liquid g gas room S solid < S liquid << S gas 15 Chemical Thermodynamics: Chaos
15 Absolute Entropy Unlike enthalpy - we have an absolute scale for entropy, Third Law of Thermodynamic: At absolute zero (0 K), a crystalline solid of any pure substance will have a Zero Entropy, S = 0 J/mol. Charles 3rd Law of Thermodynamics: At absolute zero, the entropy of a crystalline solid of a pure substance is equal to zero. 16 Chemical Thermodynamics: Chaos
16 Second Law of Thermodynamics In any spontaneous process, there is always an increase in the entropy of the universe. Entropy of the Universe is always increasing. (It is not conserved!!! ) ΔS univ = ΔS sys + ΔS surr Predict whether a process is spontaneous: ΔS univ (+) Spontaneous process. ΔS univ (0) No Tendency to occur. (@ equilib.) ΔS univ (-) Opposite event is spontaneous. Most probable micro-state is most random state. 17 Chemical Thermodynamics: Chaos
17 So why does your room eventually get clean? It is messy because nature prefers that state. Eventually it is straighten out. Why does it eventually get clean? Does this Violation th 2nd Law of Thermodynamics? Important Factor: ΔS univ (+) For 2nd law to be obeyed ΔS univ = ΔS sys + ΔS surr ΔS sys (-) but ΔS surr (+) room (-) you (+) ΔS sys << ΔS surr g ΔS univ This result in a ΔS univ (+)!!! 18 Chemical Thermodynamics: Chaos
18 Predicting Relative S Values order vs. disorder What are the relative Entropy S for various systems. 1. Temperature Change: 273K 295K 298K Cu: S, (J/mol K) 2. Phase Change: Solid Liquid Gas Na : S, (J/mol K) H 2 O : S, (J/mol K) C : S, (J/mol K) 3. Dissolution of Solid, liq, gas Solid Liq/gas Aqueous solid NaCl: S, (J/mol K) solid AlCl 3 : S, (J/mol K) liquid CH 3 OH : S, (J/mol K) gas O 2 : S, (J/mol K) gas diffusion O 2 g O 2 +N 2, (J/mol K) ΔS > 0 4. Complexity of element Li Na K Rb S, (J/mol K) 19 Chemical Thermodynamics: Chaos
19 Tabulation of ΔS: Appendix For any Thermodynamic function: Function ΔX rxn = Σ n ΔX prod - Σ n Δ X react Enthalpy: ΔH rxn = Σ n ΔH prod - Σ n ΔH react Entropy: ΔS rxn = Σ n S prod - Σ n S react Free Energy: ΔG rxn = Σ n Δ G prod - Σ n Δ G react Example: S J/mol K Be(OH) 2 (s) g BeO (s) + H 2 O (g) 22 Chemical Thermodynamics: Chaos
20 Tabulation of ΔS: Appendix For any Thermodynamic function: Function ΔX rxn = Σ n ΔX prod - Σ n Δ X react Enthalpy: ΔH rxn = Σ n ΔH prod - Σ n ΔH react Entropy: ΔS rxn = Σ n S prod - Σ n S react Free Energy: ΔG rxn = Σ n Δ G prod - Σ n Δ G react Example: Be(OH) 2 (s) g BeO (s) + H 2 O (g) S J/mol K ΔS rxn = Σ n S prod - Σ n S react ΔS rxn = [ ] ΔS rxn = J / mol K 23 Chemical Thermodynamics: Chaos
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