PC2 TP CE Hints

TUTORIAL PROBLEMS PHYSICAL CHEMISTRY 2
CHEMICAL EQUILIBRIUM
(CE-1) IS A MIXTURE AT EQUILIBRIUM?
A reaction vessel is filled with 0.300 mol H2, 0.400 mol I2, and 0.200 mol HI at 870. K and initially
at a total pressure of 1.00 bar. Is the mixture at equilibrium, given that KP for the reaction
H2(g) + I2(g) → 2 HI(g) is 870.? If not, will the amount of HI tend to increase or decrease?
GETTING STARTED: see Atkins, QMC: To. 75, and PC: Ch 6A. What is the expression for KP for
this reaction? What is the reaction quotient? How can the amounts and total pressure be used to
calculate the partial pressures?
PC2-TP-CE-1
(CE-2) DISSOCIATION REACTION IN A PERFECT GAS MIXTURE
Consider the dissociation reaction of N2O4 in the gas phase:
N2O4 → 2 NO2 (CE-2.1)
The equilibrium constant for the reaction as written in Eq. (CE-2.1) at 100.0∘Cis given as
KP = 15.04. Assume perfect gas behavior.
(a) Show that the partial pressures of N2O4 and NO2 in the reaction mixture at any time during the
reaction can be written as Eqs. (CE-2.2) and (CE-2.3):
nN0 2 O4 − x
PN2 O4 = Ptot (CE-2.2)
n N0 2 O4 + n NO
0
2
+x
0
nNO 2
+ 2x
PNO = Ptot (CE-2.3)
2 n N0 2 O4 + n NO
0
2
+x
Here, Ptot is the total pressure of the reaction vessel, and n N0 is the initial amount of N2O4 in the
2 O4
reaction mixture, with similar meaning for the other amounts.
What is x? On which law are these expressions based and what is the physical justification of this
law?
GETTING STARTED: See Atkins, QMC: To. 73 and 75, and PC: Ch 6A.1, Ex. 6A.2, and Ch 6B.
PC2-TP-CE-2
(b) Write down the equilibrium constant Ka for this reaction in terms of the activities of the
reactants and products, and show that at constant temperature and pressure, under the assumption
made in (a), equilibrium is reached when Eq. (CE-2.4) is satisfied:
2
PNO 2 0 /RT
= e −Δr μ (CE-2.4)
PN2 O4 P0
GETTING STARTED: Use the stoichiometric coefficients of the reaction to write down the Ka.
Then think about how the assumption in (a) can be used to express the activities in terms of
pressures. Next, connect the equilibrium constant to the Gibbs energy of reaction.
(c) At some point in time, the partial pressures of N2O4 and NO2 in the reaction mixture are 183.8
and 16.2 kPa, respectively. The temperature is100.0∘C. Will the reaction proceed toward product
(NO2) or reactant? Confirm your analysis by calculating the Δr G for this reaction mixture.
GETTING STARTED: Calculate the so-called reaction quotient and compare it to the equilibrium
constant. Calculate Δr G from Q and KP.
(d) Write out the equilibrium constant KP as a function of x, and show that the solution for x is
given by Eq. (CE-2.5), if it is given that the initial amounts of N2O4 and NO2 in the reaction
mixture are n 0 and 0, respectively, while the mixture is at total pressure Ptot.
1/2
( KP + 4Ptot /P 0 )
KP
xeq = n 0 (CE-2.5)
GETTING STARTED: Use Eqs. (CE-2.2-4) and write out the terms, and simplify as much as
possible. Then, solve for x. xeq is the value when equilibrium is reached.
PC2-TP-CE-3
xeq
(e) Make a sketch of versus Ptot (the total pressure of the mixture) at 100.0∘C. Does your result
n0
agree with Le Châtelier's principle?
GETTING STARTED: If you choose n 0 = 1 mol and express Ptot in bar, you can easily calculate
the value of xeq for three pressures or so. (When Ptot = 0, the value of xeq follows immediately.) A
sketch can then be made without much effort.
PC2-TP-CE-4
(CE-3) THERMODYNAMIC DATA FOR A REACTION FROM TEMPERATURE
DEPENDENCE OF THE EQUILIBRIUM CONSTANT.
It is experimentally determined that KP of a given reaction doubles upon increasing the temperature
from 300. K to 400. K.
(a) Calculate the standard enthalpy of reaction, under the assumption that the standard enthalpy of
reaction is independent of temperature.
GETTING STARTED: see Atkins, QMC: To. 75, and PC: Ch 6B.2
What is the basic relation between the equilibrium constant and temperature? Why do you not need
the absolute values of the equilibrium constants at the two temperatures given?
(b, extra challenge) Is it possible to also determine the standard entropy of reaction, Δr S ⊖? If yes,
what is the value of Δr S ⊖ and is this exact or an estimate?
GETTING STARTED: Think of fundamental thermodynamic relations between thermodynamic

quantities.
(CE-4) PREDICTING AN EQUILIBRIUM CONSTANT.
The standard enthalpy of reaction of a particular reaction at 1,000. K is known to be

34.78 kJ ⋅ mol−1. Given that the equilibrium constant is K = 0.236 at 800. K, estimate K at 1,200.
K. In your answer, state the relation(s) and assumption(s) you are making. Discuss the trend in K in
terms of the principle of Le Châtelier.
GETTING STARTED: see Atkins, QMC: To. 75, and PC: Ch 6B.2
What is the basic relation between the equilibrium constant and temperature?
PC2-TP-CE-5
(CE-5) REVISITING THE DISSOCIATION REACTION IN A PERFECT GAS MIXTURE
Consider the dissociation reaction of N2O4 in the gas phase studied in TP-CE-2:
N2O4 → 2 NO2 (CE-2.1)
(a) The equilibrium constant at 120.0∘C is measured to be 38.06. Give a reasonable estimate for the
standard enthalpy of reaction. Clearly indicate which assumption(s) you are making. Use data from
TP-CE-2 if you need them.
GETTING STARTED: How does the equilibrium constant (or Gibbs energy of reaction) depend on
temperature in general? Is there a reasonable assumption that can be made so that the data you have
available can be used to estimate the standard enthalpy of reaction?
(b) Assuming the standard enthalpy of reaction does not depend on the temperature, predict the
equilibrium constant for the reaction at 80.0∘C. Discuss the trend in equilibrium constant in the light
of Le Châtelier’s principle.
GETTING STARTED: Compare to your approach in (a).
PC2-TP-CE-6
(CE-E1) GAS PHASE DISSOCIATION EQUILIBRIUM OF WATER
In the gas phase, at 2,000. K and 1 bar, 0.53% of water is dissociated. It is found that at 2,100. K
and 1 bar, 0.88% of the water is dissociated.
(a) Write down the reaction equation for the dissociation of water.
(b) Calculate the standard enthalpy of dissociation of water (assuming it is independent of

temperature).
HINT: start by expressing the percentage of dissociation in terms of the extent of the reaction.
(CE-E2) VAPOR PRESSURE AND STANDARD ENTHALPY OF REACTION
The equilibrium vapor pressure P (in Pa) of H2 gas over a solid mixture of U(s) and UH3(s)
between 450. and 715. K is given by the empirical expression:
ln P/P ⊖ = A + B /T + C ln T ; A = 69.32,B = − 1.464 × 10 4 K, C = − 5.65
(a) Derive an expression for the standard enthalpy of formation of UH3(s) as a function of
temperature.
(b) Give the expression for the standard heat capacity for the formation reaction at constant pressure
Δr CP⊖ for this reaction.
PC2-TP-CE-7

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TUTORIAL PROBLEMS PHYSICAL CHEMISTRY 2

(CE-1) IS A MIXTURE AT EQUILIBRIUM?

Consider the dissociation reaction of N2O4 in the gas phase:

N2O4 → 2 NO2 (CE-2.1)

reaction mixture, with similar meaning for the other amounts.

agree with Le Châtelier's principle?

sketch can then be made without much effort.

GETTING STARTED: Think of fundamental thermodynamic relations between thermodynamic

(CE-4) PREDICTING AN EQUILIBRIUM CONSTANT.

The standard enthalpy of reaction of a particular reaction at 1,000. K is known to be

N2O4 → 2 NO2 (CE-2.1)

GETTING STARTED: Compare to your approach in (a).

(b) Calculate the standard enthalpy of dissociation of water (assuming it is independent of

(CE-E2) VAPOR PRESSURE AND STANDARD ENTHALPY OF REACTION

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