Renee Y. Becker Valencia Community College CHM 1046 Thermochemistry Renee Y. Becker Valencia Community College CHM 1046

Enthalpies of Chemical Change: Often called heats of reaction (DH) units kJ Endothermic: Heat flows into the system from the surroundings and DH has a positive sign. Exothermic: Heat flows out of the system into the surroundings and DH has a negative sign.

Are the following reactions endothermic or exothermic Are the following reactions endothermic or exothermic? Favorable or unfavorable? C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) DH = –2219 kJ CH3Cl(g) + HCl(g)  CH4(g) + Cl2(g) DH = 98.3 kJ

Entropy The measure of molecular disorder in a system is called the system’s entropy; this is denoted S. Entropy has units of J/K (Joules per Kelvin). DS = Sfinal – Sinitial Positive value of DS indicates increased disorder. Negative value of DS indicates decreased disorder.

Entropy Second Law of Thermodynamics: Reactions proceed in the direction that increases the entropy of the system plus surroundings. A spontaneous process is one that proceeds on its own without any continuous external influence. A nonspontaneous process takes place only in the presence of a continuous external influence.

Predict whether DS is likely to be positive or negative for each of the following reactions. a. 2 CO(g) + O2(g)  2 CO2(g) b. 2 NaHCO3(s)  Na2CO3(s) + H2O(l) + CO2(g) c. C2H4(g) + Br2(g)  CH2BrCH2Br(l) d. 2 C2H6(g) + 7 O2(g)  4 CO2(g) + 6 H2O(g)

To decide whether a process is spontaneous, both enthalpy and entropy changes must be considered: Spontaneous process: Decrease in enthalpy (–DH). Increase in entropy (+DS). Nonspontaneous: Increase in enthalpy (+DH). Decrease in entropy (–DS).

Free Energy Gibbs Free Energy Change (DG): Weighs the relative contributions of enthalpy and entropy to the overall spontaneity of a process. DG = DH – TDS DG < 0 Process is spontaneous DG = 0 Process is at equilibrium DG > 0 Process is nonspontaneous

Which of the following reactions are spontaneous under standard conditions at 25°C? a. AgNO3(aq) + NaCl(aq)  AgCl(s) + NaNO3(aq) DG° = –55.7 kJ b. 2 C(s) + 2 H2(g)  C2H4(g) DG° = 68.1 kJ c. N2(g) + 3 H2(g)  2 NH3(g) DH° = –92 kJ; DS° = –199 J/K

Equilibrium (DG = 0): Equilibrium is the point where DG = DH – TDS = 0 Estimate of the temperature at which a reaction becomes spontaneous (set DG =0) T = DH / DS

2 NH3(g)  N2(g) + 3 H2(g) DH = 92.0 kJ DS = 199 J/K Is this reaction spontaneous @ 25C? If not, at what temperature does this reaction become spontaneous?