Chapters 17,18,19
W
# of micro states
Calculate ΔG^0 for the following reactions: (a) 2Mg(s) + O2 (g) ---> 2MgO(s) (b) 2SO2 (g) + O2 (g) ---> 2SO3(g) (c) 2C2H6(g) + 7O2(g) ---> 4CO2(g) + 6H2O (l)
(a) -1139 kJ/mol (b) -140.0 kJ/mol (c) -2935 kJ/mol
Using the data in Appendix 3, calculate the standard entropy changes for the following reactions at 25C: (a) H2(g) + CuO(s) ---> Cu(s) + H2O(g) (b) 2Al(s) + 3ZnO(s) ---> Al2O3(s) + 3Zn(s) (c) CH4(g) +2O2(g) ---> CO2(g) + 2H2O(l)
(a) 47.5 J/K-mol (b) -12.5 J/K-mol (c) -242.8 J/K-mol
Find the temperatures at which reactions with the following ΔH and ΔS values would become spontaneous: (a) ΔH = -126 kJ/mol, ΔS = 84 J/K-mol (b) ΔH = -11.7 kJ/mol, ΔS = -105 J/K-mol
(a) at all temperatures (b) below 111K
State whether the sign of the entropy change expected for each of the following processes will be positive or negative, and explain your predictions: (a) PCl3(l) + Cl2(g) ---> PCl5(s) (b) 2HgO(s) ---> 2Hg(l) + O2(g) (c) H2(g) ---> 2H(g) (d) U(s) + 3F2(g) ---> UF6(s)
(a) ΔS < 0 (b) ΔS > 0 (c) ΔS > 0 (d) ΔS <0
The equilibrium constant Kp for the reaction: H2 (g) + CO2(g) <---> H2O(g) + CO(g) is 4.40 at 2000K. (a) Calculate ΔG^0 for the reaction (b) Calculate ΔG for the reaction when partial pressures are P(H2) = 0.25 atm, P(CO2) = 0.78 atm , P(H2O) = 0.66 atm, P (CO) = 1.20 atm
-24.6 kJ/mol
The equilibrium constant Kp for the reaction: CO(g) + Cl2(g) <------> CoCl2(g) is 5.62 x 10^35 at 25C. Calculate ΔGf^0 for COCl2 and 25C
-341 kJ/mol
Standard Entropy
1 atm 298 K (25C)
Boltzmann Constant
1.38x10^23 J/K
Calculate ΔG and Kp for the following equilibrium reaction at 25C: 2H2O(g) <----> 2H2(g) + O2(g)
4.572 x 10^2 kJ/mol
For the auto ionization of water at 25C: H2O(l) <------> H+ (aq) + OH- (aq) Kw is 1.0 x 10^-14 ; what is ΔG for process?
8.0 x 10^1 kJ/mol
how to calculate E^0
E^0cell= E^0 cathode - E^0anode
S
Entropy
Third Law of Thermodynamics
Entropy of a perfect crystalline substance is zero at absolute zero of temperature
S=klnW
Entropy=(1.38x10^-23 J/K)lnW
E^0=( RT / nF) lnK
F= 95600
Gibbs Free Energy Change in Gibbs Free Energy
G= H- TS ΔG=ΔH-TΔS
ΔG>0
The reaction is non-spontaneous. The reaction is spontaneous in the opposite direction
ΔG<0
The reaction is spontaneous in the forward direction
ΔG=0
The system is at equilibrium. There is no net change
EMF (electromotive force)
a measure of voltage
Arrange the following substances (1 mole of each) in order of increasing entropy at 25C: (a) Ne (g) (b) SO2 (g) (c) Na (s) (d) NaCl (s) (e) H2 (g)
c d e a b
anode
electrode at which oxidation occurs
cathode
electrode at which reduction occurs
what does II mean?
salt bridge
E^0
standard reduction potential; voltage associate with a reduction reaction at an electrode when all solutes are 1 M and all gases are at 1 atm
Electrochemistry
the branch of chemistry that deals with the interconversion of electrical energy and chemical energy
Second Law of Thermodynamics
the entropy of the universe increases in a spontaneous process and remains unchanged in an equilibrium process
Galvanic Cell
the experimental apparatus for generating electricity through the use of a spontaneous reaction
cell voltage or cell potential
voltage across the electrodes of a galvanic cell
How do we calculate the standard free energy of a reaction?
ΔG(rxn)= [ΔGmoles of products] - [ΔGmoles of reactants]
Relationship between ΔG and ΔG^0
ΔG= ΔG^0 + RT ln Q
ΔG at equilibrium
ΔG^0 = -RT ln K
The standard enthalpy of formation and the standard entropy of gaseous benzene are 92.3 kJ/mol and 269.2 J/K-mol. Calculate ΔH and ΔS and ΔG for the process at 25C: C6H6(l) ----> C6H6(g)
ΔH = 33.89 kJ/mol ΔS = 96.4 J/mol ΔG = 5.2 kJ/mol
How do we calculate the standard enthalpy of a reaction?
ΔS(rxn)= [cS(C) + dS(D)] - [aS(A) + bS(B)] or ΔS(rxn)= { (sum of products) - { (sum of reactants)
Relationship between ΔS(surr) and ΔH(sys)
ΔS(surr)=-ΔH(sys) / T
Consider the following reaction at 298K: 2H2(g) + O2(g) ---> 2H2O(l) ΔH^0= -571.6 kJ/mol Calculate ΔS(sys), ΔS(surr), and ΔS(univ) for reaction
ΔS(sys) = -327 J/K-mol ΔS(surr) = 1918 J/K-mol ΔS(univ) = 1591 J/K-mol
Equilibrium Process
ΔS(univ)=ΔS(sys)+ΔS(surr)=0
Spontaneous Process
ΔS(univ)=ΔS(sys)+ΔS(surr)>0