Problem Set 2

PROBLEM SET 2
CHEMICAL THERMODYNAMICS
I. Basic Concepts
1. System, surrounding, and universe
2. Open, closed, and isolated systems
3. Intensive and extensive properties of a system
4. State of a system state and non-state functions
5. Equation of state
6. Paths and processes isobaric, isochoric, isothermal, adiabatic, reversible,
irreversible
7. Work
8. Heat
8.1 Heat at constant pressure (qp) and heat at constant volume (qv)
8.2 Molar heat capacity at constant pressure (Cp) and at constant volume (Cv)
II. First Law of Thermodynamics
1. Law of conservation of energy
2. Concept of internal energy (U) and enthalpy (H)
3. Thermochemistry
3.1 Calorimetry
3.2 Bomb calorimeter and constant pressure calorimeter
3.3 Hesss Law
3.4 Heat of reaction
3.5 Heat of physical transformation
III. Second Law of Thermodynamics
1. Spontaneous and non-spontaneous process
2. Entropy (S)
2.1 Thermodynamic approach to entropy
2.2 Statistical approach to entropy
3. Free energy (G) and spontaneity
4. S and G for
4.1 chemical reactions
4.2 physical transformations
IV. Third Law of Thermodynamics
V. U, H, S, and G of coupled reactions
CHEMICAL EQUILIBRIUM
I. Approaches to Equilibrium
1. Kinetics
2. Thermodynamics
II. Molecular Equilibrium
1. Free Energy change (G) and equilibrium constant
2. Activity quotient (Q) and the equilibrium constant (K)
3. K of coupled reactions
1
4. Kp or Kc and equilibrium concentrations

5. Factors affecting equilibrium
QUESTIONS/PROBLEMS
I.
Each of the following numbers consists of two quantities, one in column I and
another in column II. You are to compare the two quantities and choose
A
B
C
D
1.
2.
3.
if the quantity in column I is greater than that in column II

if the quantity in column I is less than that in column II
if the two quantities are equal
if the relationship cannot be determined from the given information
Column I
Column II
A gas is heated from T1 to T2
heat absorbed at constant V
heat absorbed at constant P
The exothermic reaction: A(s) + B(g) C(g) + heat
Ho
Uo
H of vaporization of X
4.
For a spontaneous process

S of the system
5.
H of fusion of X
S of the surroundings
A system undergoes a cyclic process

work done in the process
heat involved in the process
6.
Kp
The given reaction reaches equilibrium at 500 K

C(s, graphite) + O2(g) CO2(g)
Kc
7.
The equilibrium:
P4(g) + 6Cl2(g) 4PCl3(g)
is established by adding equimolar amounts of P4 and Cl2
to an evacuated flask
[P4]equilibrium
[Cl2]equilibrium
8.
The standard free energy change is negative for

R P
[R]equilibrium
[P]equilibrium
9.
When A was added to the reaction: X Y

the rate of formation of Y increased.
Continued addition of A, however, did not have an effect on [Y].
H
TS
II. Choose the BEST answer.

1. For any chemical reaction carried out in any manner, the quantity of heat associated
with the reaction is given by the relationship:
A) U + w
B) U w
C) qv
D) qp
2
2. Ten (10.0) g of steam at 100 oC and 100.0 g of ice at 0 oC are added to 100.0 g of
liquid water at 20 oC in a perfectly insulated container. Which of the following will
happen?
Heat of fusion of ice = 6.02 kJ/mol; Heat of vaporization of H2O(l) = 40.7 kJ/mol
A) The mixture will start to boil
C) All the ice will melt
B) All of the liquid water will freeze
D) a mixture of ice and liquid will remain
3. If a system is doing work while liberating heat, what will happen to the internal energy
of the system?
I. It will remain constant
IV. It will be equal to enthalpy
II. It will increase
V. It will be equal to the heat at constant volume
III. It will decrease
A) I, IV
B) II
C) II, IV, V
D) IV
E) V
For numbers 4 and 5, consider the equilibrium reaction:
S(s) + 3/2 O2(g)
SO2(g) + 99.1 kJ
4.
The equilibrium constant was observed to decrease when certain processes were
carried out. Which of the following must have been done?
A) temperature was increased
C) energy of activation was increased
B) catalyst was added
D) volume was decreased
5. The [SO2] increased. What was/were the process/es?

I. The temperature was decreased
III. Surface area was increased
II. [S] was increased
IV. Volume of the container was increased
A) I
B) I, II
C) II, III
D) IV
E) II, IV
6. The system: X + 2Y C, is at equilibrium when the concentration of X is 1.0 M.
Enough X was added to raise its concentration temporarily to 1.4 M. What is the most
probable equilibrium concentration of X?
A) 0.8 M
B) 1.0 M
C) 1.3 M
D) 1.4 M
E) 1.6 M
7. It is desired to establish the equilibrium: FeO(s) + CO(g) Fe(s) + CO2(g). Which
of the following combinations when placed in an empty container would NOT work?
I. FeO, CO
II. FeO, CO, Fe
III. Fe, CO
IV. FeO, Fe, CO2
A) I, II
B) III
C) III, IV
D) II
E) IV
8. Suppose you want to remove water vapor from a container. Using the information
below, which is the best reagent for this purpose?
Cu(s) + H2O(g) CuO(s) + H2(g)
K = 2 x 10-8
CO(g) + H2O(g) CO2(g) + H2(g)
K = 1 x 102
CO(g) + H2(g) C(s) + H2O(g)
K = 2 x 1019
2H+(aq) + SO42-(aq) H2O(g) + SO3(g)
K = 1 x 10-28
A) Cu
B) CO
C) C
D) SO3
9. Equilibrium is established in the reaction: 2SO2(g) + O2(g) 2SO3(g) at a
temperature at which Kc = 100. If the number of moles of SO2 in the equilibrium
mixture is equal to number of moles of SO3, which of the following is correct?
A) The number of moles of O2 is also equal to the number of moles of SO2.
B) The number of moles of O2 is half the number of moles of SO2.
C) [O2] = 0.01 M
D) [O2] may have any of several values.
3
10. At a certain temperature the reaction: CO(g) + H2O(g) CO2(g) + H2(g), attains
equilibrium. Suppose 0.40 mol CO and 0.5 mol H2O are placed in a 2.0-liter container.
What will be the equilibrium concentration of CO?
A) 0.4 M
B) 0.5 M
C) 0.2 M
D) less than 0.20 M
E) more than 0.2 M but less than 0.25 M
11. Which of the following is/are TRUE for the reaction: X + Y Z
A) The reaction is at equilibrium.
B) The forward reaction proceeds spontaneously.
C) The backward reaction proceeds to equilibrium.
D) The reaction is very fast.
G = -240 kJ
III. Solve the following problems.

1. A gas expanding against a constant pressure of 2.0 atm from 5.0 L to 15.0 L absorbs
300 J of heat. What happens to the internal energy of the gas?
2. The heats of combustion of C(graphite), H2(g) and CH4(g) at 298 K and 1 atm are -393
kJ/mol, -286 kJ/mol, and -892 kJ/mol, respectively. What is the enthalpy change for
the reaction in which 1 mole of CH4 is formed from graphite?
3. The combustion of 0.14 g of methanol (CH3OH) at constant pressure raises the
temperature of a calorimeter by 0.222 oC. The heat capacity or calorimeter constant is
1.5 kJ/oC. Calculate H and U for the reaction:
CH3OH(g) + 3/2 O2(g) CO2(g) + 2H2O(l)
4. Use the data below to determine whether the formation of sucrose, C12H22O11(s), from
CO2(g) and H2O(l) is spontaneous at standard state.
o
Hf (kJ/mol)
So (J/K mol)
12CO2(g) + 11H2O(l)
-393
-286
214
70
C12H22O11(s) + 12O2(g)
-2222
0
360
205
5. One mole of steam is condensed reversibly to liquid water at 100 oC and 1 atm. The
heat of vaporization of water is 2,256 J/g. Assuming that steam behaves as an ideal
gas, calculate w, q, U, H, S, and G for the process.
6. The combustion of n-butane is described by the reaction:
C4H10(g) + 13/2 O2(g)
4CO2(g) + 5H2O(l)
H = -2877 kJ
How many grams of n-butane must be burned to heat 1.00 kg of water from 20.0 oC to
30.0 oC? The specific heat of water is 4.184 J/g oC.
7. A. Calculate the calorimeter constant from the following data:
Temperature of 50 mL warm water
Temperature of 50 mL cold water
Equilibrium temperature
Specific heat of water
Density of water
37.9 oC
20.9 oC
29.1 oC
4.184 J/g oC
1.0 g/mL
4
B.
A reaction between 50 mL of 0.010 M AB and 50 mL of 0.015 M CD was

performed in the above calorimeter. If the temperature was observed to
increase by 0.65 oC, calculate the H per mole of limiting reactant for the
reaction.
AB(aq) + CD(aq) AD(aq) + CB(aq)
Assume that the density and the specific heat of the reacting and the resulting
solutions are the same as that of water since they are dilute.
8. Calculate the H for the following reaction using the given bond energies:
H2O(g) + F2(g)
Bond
Bond energy (kJ/mol)
OH
464
2HF(g) + O2(g)
FF
158
HF
569
O=O
498
9. Predict the entropy change (increase, decrease, or remain the same) for each of the
following reactions:
A) N2(g) + O2(g) 2NO(g)
B) 2Mg(s) + O2(g) 2MgO(s)
C) Ag+(aq) + Cl-(aq) AgCl(s)
D) 2H2O2(l) 2H2O(l) + O2(g)
10. Calculate the equilibrium constant for the reaction: C(s) + 2H2(g)
which Ho = -74.84 kJ and So = 80.67 J/K at 25 oC.
CH4(g), for
11. For the reaction: H2(g) + I2(g) 2HI(g), Go = -10.0 kJ at 25 oC. Towards
which direction will the reaction proceed spontaneously when H2 at 0.10 atm, I2 at 0.2
atm and HI at 10 atm are reacted at 25 oC? Assume all species behave like ideal gas.
12. A 1.0-L vessel containing the equilibrium mixture: CO(g) + Cl2(g) COCl2(g) was
found to contain 0.40 mol of COCl2, 0.10 mol of CO, and 0.50 mol of Cl2.
A) What is the equilibrium constant Kc?
B) If 0.30 mol of CO is added at constant temperature to the mixture, what will be the
new equilibrium concentration of each component?
13. The reaction: C(s) + CO2(g) 2CO(g), has a Kp value of 14.11 at 1123 K. CO2 is
supplied initially at 0.50 atm then kept in contact with graphite at 1123 K until the
reaction has come to equilibrium. What is the total pressure of the equilibrium
mixture?

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PROBLEM SET 2

4. Kp or Kc and equilibrium concentrations

if the quantity in column I is greater than that in column II

For a spontaneous process

A system undergoes a cyclic process

The given reaction reaches equilibrium at 500 K

The standard free energy change is negative for

When A was added to the reaction: X Y

II. Choose the BEST answer.

5. The [SO2] increased. What was/were the process/es?

III. Solve the following problems.

A reaction between 50 mL of 0.010 M AB and 50 mL of 0.015 M CD was

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