Hess's Law

Given the following data:

2O3(g) 3O2(g)
O2(g) 2O(g)
NO(g) + O3(g) NO2(g) + O2(g)

H = - 427 kJ
H = + 495 kJ
H = - 199 kJ

a. Calculate the H of the reaction

NO(g) + O(g) NO2(g)
b. Determine S of the reaction given the following standard entropy values at 25C.
Substance
S(J/Kmol)
NO(g)
211
O(g)
161
NO2(g)
240
c. Determine G of the reaction at 25C.
d. Is the reaction spontaneous or non-spontaneous? Determine when will it be spontaneous or nonspontaneous.
Solution:
a. Manipulating the given equations:
(3O2(g) 2O3(g)
H = + 427 kJ)
(2O(g)
O2(g)
H = - 495 kJ)
NO(g) + O3(g) NO2(g) + O2(g)
H = - 199 kJ
NO(g) + O(g) NO2(g)
H = - 233 kJ
b. Using the formula for Srxn:
Srxn = np Sproducts - nr Sreactants
= 1 mol(240 J/Kmol) 1 mol(211 J/Kmol + 161 J/Kmol)
= -132 J/K
c. G = H - TS
Substituting the values obtained from a and b,
G = -233 kJ (298.15 K)(-132 J/K)(1kJ/1000J)
G = -193.64 kJ
d. Since G < 0, the reaction above is non-spontaneous. For it to be spontaneous,
H - TS > 0
H/S > T
(-233 kJ)/(-0.132 kJ) > T
T < 1765.15 K or 1492C
Non-standard Thermodynamics
(From http://www.cengage.com/chemistry/discipline_content/owl/support/chapters/owlbook_ch19.pdf)
Use standard thermodynamic data to calculate G at 298.15 K for the following reaction,
assuming that all gases have a pressure of 22.51 mm Hg.
4 HCl(g) + O2(g) 2H2 O(g) + 2Cl2(g)

Solution: You are asked to calculate Grxn at 298.15 K.

You are given the balanced chemical equation, the pressure of each gas, and the Gf data for each
substance.
First, calculate G using Gf values. Recall that the standard free energy of formation for elements is
zero.
G = np Gproducts - nr Greactants
= (2 mol)(Gf[H2O(g)]) (4 mol)(Gf[HCl(g)])
= (2 mol)(228.6 kJ/mol) (4 mol)(95.3 kJ/mol)
= 76.0 kJ
Use the formula G = G + RTlnQ to solve for G.
For a gas phase reaction, Q is expressed in terms of partial pressures (atm).

Finally, substitute these values, along with temperature and the ideal gas constant, into the equation G
= G + RTlnQ and calculate G. We will use units of kJ/mol for the calculated G value to indicate
the standard free energy change is for the reaction as written above.
G = G + RTlnQ
= (76.0 kJ/mol) + (8.3145 10^-3 kJ/Kmol)(298.15 K)[ln(33.76)]
= 76.0 kJ/mol + 8.72 kJ/mol
= 67.3 kJ/mol
The negative G value tells us that the reaction is not at equilibrium and must proceed in the forward
direction to reach equilibrium.