WARM-UP EXERCISES (PHYSCHEM)

Problem 1 Four glass bottles are connected to each other according to the drawing below. Initially all switches are
closed. The bottles are filled with hydrogen, oxygen, nitrogen and argon, respectively. Each bottle contain the same
mass of gas and the system is thermostated by a 25 °C isolated reservoir filled an ideal gas. The heat absorbed or
delivered by the reservoir can be measured by an apparatus. The first gas bottle is connected to the reservoir by a
pressure equalizer switch which is initially closed. If the switch is open it equalizes the pressure between the bottle
and the reservoir. There is a Pt catalyst on the wall of the fourth bottle which is initially hermetically separated
from everything else. In the initial equilibrium the pressure in all bottles as well as the in the termostat is 1 bar. All
gases and mixtures can be considered ideal.
× • Circles are the gas bottles, the large square is the reservoir
(thermostat).
H2 Ar * • 1, 2, 3, 4: switches, numbered in the order of opening.
4.
• ×: pressure equalizer.
1. 2.
• *: catalyst, initially hermetically separated from the gases.
3.
N2 O2 a) The volume of the bottle filled with hydrogen is 0.1 m3.
Calculate the volume of the other three bottles.

Legend (top view)

We open the first switch and wait to reach equilibrium in a reversible and isothermal process. Then we open the
second switch and wait a day again. Afterwards we open the third switch and wait a day again. Finally the fourth switch
is opened and the equilibrium is reached after waiting one further day. The heat transfer measured is recorded after
each process.
b) Calculate the factor by which the partial pressure of argon is multiplied in each step.
There is only one plausible chemical reaction in the system obtained after opening all the switches. This reaction has
a large kinetic barrier thus it does not initialize without excitation or catalyst.
c) Calculate the standard Gibbs free energy change Data ΔfHϴ/kJ/mol ΔfSϴ / J/mol K
of this reaction.
H2O (g) -241.8 -44.5
d) Calculate the partial pressure of the reactants in
the system. H2O (f) -285.8 -163.3

We set the temperature of the thermostat to 200 °C and leave it alone to reach equilibrium. For security reasons we
open the pressure equalizer thus the pressure in the systems will be the same as in the termostat (under equilibrium
conditions).
e) Calculate the standard Gibbs free energy change of this reaction at 200 °C.
After reaching the equilibrium a mechanic comes to our lab and his magnet unintentionally hits our reactor causing a
spark which initializes the reaction. The momentary reaction runs in negligible time without having time to change the
volume of the reactor or equalize the pressure. The sudden explosion is followed by a relaxation to equilibrium while
the temperature and the pressure of the reservoir remain unchanged. By the time we get back to the lab we are
surprised to see that heat transfer was measured in the thermostat. We shout at the mechanic for a while for spoiling
our experiment and start everything all over again. As we do not need the mixing entropies again those data are not
recorded. After five days we become ready to continue our experiment from 200 °C again.
f) Could we make our repeated experiment faster? Why?
In the next step we make the catalyst accessible allowing it to run the chemical reaction reversibly.
g) Calculate the partial pressure of the reactants and products of the resulting system at 200 °C.
Finally the catalyzer is blocked again and the system (and reservoir) is cooled down to 25 °C. Vapour pressure of water
at 25 °C is 3.17 kPa.
 h) Calculate the partial pressure of the reactants and products of the resulting system at 25 °C.
Problem 2 The degree of dissociation of carbon dioxide is  = 2.0·10−7 at 1000 K and 101325 Pa.
a) Give the balanced reaction equation!
b) Calculate Kx for the reaction at the given temperature and pressure!
c) Calculate Kp for the reaction at the given temperature and pressure!
d) Calculate Ka for the reaction at the given temperature and pressure!
e) Calculate ΔrG for the reaction at the given temperature and pressure!
f) Calculate Kx for the reaction at the given temperature at 0.5 bar!
g) Calculate Kp for the reaction at the given temperature at 0.5 bar!
h) Calculate Ka for the reaction at the given temperature at 0.5 bar!
i) Calculate ΔrG for the reaction at the given temperature at 0.5 bar!
j) Calculate  for the reaction at the given temperature at 0.5 bar!
k) Is the result in accordance with the LeChatelier principle?
l) Calculate  for the reaction at the given temperature at 2 bar!
m) Is the result in accordance with the LeChatelier principle?
Problem 3 Burning of alkanes is one of the most important chemical methods to obtain energy in form of heat.
Consider the overall chemical equation in the form CH4 + O2 = CO2 + H2O.
a) Balance the above equation. ΔfHϴ / kJ/mol ΔfGϴ / kJ/mol (25 °C)
b) Calculate the standard Gibbs energy of the above H2O(g) -241.8 -228.6
reaction at 400 °C. H2O(l) -285.8 -237.1
ϴ
Data: S (H2) = 130.7 J/mol K CO2(g) -393.5 -394.4
CH4(g) -74.8 -50.7

Problem 4 The standard enthalpy change of the reaction CaCl2·NH3(s) = CaCl2(s) + NH3(g) is constant 78.0 kJ/mol
between 350 and 500 K. The standard Gibbs free energy of the reaction is 13.6 kJ/mol at 400 K.
a) Calculate the equilibrium constant at 400 K.
b) Calculate the equilibrium constant at 440 K.
c) Give the partial equilibrium pressure of ammonia at 440 K.
d) Calculate the volume change of the reaction at 440 K and 14 kPa.
e) Estimate the temperature where the equilibrium constant of the above rection is 1.
Problem 5 The decomposition of formaldehyde results in carbon-monoxide and hydrogen gases.
a) Write the balanced equation for the ΔfHϴ / kJ/mol Sϴ / J/mol K
decomposition.
H2CO(g) -109 219
b) Calculate the reaction enthalpy, entropy and CO(g) -111 198
Gibbs-energy at 500 K.
H2(g) 131
c) Calculate Kp and Kx at 500 K and 1 bar.

d) A vessel is thermostated at 500 K and the pressure is kept constant at 1 bar. Calculate the equilibrium partial
pressure of H2CO(g) in this vessel.
e) Calculate the equilibrium partial pressure of H2CO(g) in the vessel if it also contains an inert gas (nitrogen) with
partial pressure 0.9 bar.
 f) Calculate the equilibrium partial pressure of H2CO(g) in the vessel at 1 Mbar.
Problem 6 Calculate the standard electrode potential for the Fe3+ (aq)+ e-→Fe2+ (aq) reaction knowing that
Fe3+ (aq)+ 3 e-→Fe (sz) -0.04 V
Fe2+ (aq)+ 2 e-→Fe (sz) -0.44 V
Problem 7 The permanganate oxidation system is rather complicated: it has many oxidation states and precipitation
processes. At pH = 0 the oxidation states are the following:

It is known, that at low pH permanganate can be reduced to Mn2+, in neutral medium to MnO2 and under strongly
alkaline condition it stops at MnO42-.
a) Write down the equations of the three processes!
b) Calculate their standard potentials at pH = 1.
c) Calculate their standard potentials at pH = 7.
d) Calculate their standard potentials at pH = 14.
Problem 8 We mix a solution of K2S2O8 (0.1 mol/dm3) with equal volume of KI solution (0.2 mol/dm3).
a) Write the balanced equation of the reaction.
b) Calculate the standard cell potential of the reaction.
c) Calculate the standard Gibbs energy of the reaction.
d) Calculate the electrode potentials when 1, 10, 25, 50, 75, 90, 99, 100% of K2S2O8 has reacted.
e) Calculate the cell potential at these points.
Some data:
S2O82- + 2 e- → 2 SO42- 2.05 V
I2 + 2 e- → 2 I- 0.54 V
Problem 9 In the Standard Calomel Electrode (SCE) the electrode reaction is Hg2Cl2 (s) + 2 e- → 2 Hg (l) + 2 Cl- (aq).
The solubility of Hg2Cl2 (s) is 0.2 mg in 100 cm3.
Hg22+ + 2 e- → 2 Hg 0.79 V
Cl2 + 2 e- → 2 Cl- 1.36 V
Hg2+ + 2 e- → Hg 0.86 V
2 Hg2+ + 2 e- → Hg22+ 0.92 V
a) Calculate the electrode potential of the Standard Calomel Electrode (SCE).
b) Calculate the electrode potential of the (non-standard) calomel electrode in 0.1 mol/dm3 KCl solution.
Problem 10 Phenolftalein is a well known acid-base indicator (colorless – magenta). In strongly alkaline medium it
becomes colorless again, but this reaction is not reversible. The following data was recorded for a solution at
pH = 13.8.
a) Calculate the order of phenolftalein in the reaction.
b) Calculate the initial effective rate of the reaction.
c) Calculate the half-life of phenolftalein.
 d) What half-life would you measure in a solution with 0.006 M of phenolftalein?
e) What half-life would you measure in a solution with pH = 13.9?
c/M t/s
0.0050 0.0
0.0045 10.5
0.0040 22.3
0.0035 35.7
0.0030 51.1
0.0025 69.3
0.0020 91.6
0.0015 120.4
0.0010 160.9

Problem 11 Iodide ions catalyze the decomposition of [H2O2]0/M [I-]0/M v0/Ms–1

H2O2 in aqueous solution. In order to determine
1. 1.0 x 10-2 2.0 x 10-3 2.3 x 107
the order of the reactants the initial reaction rate
was measured at different concentrations. 2. 2.0 x 10-2 2.0 x 10-3 4.6 x 107
3. 3.0 x 10-2 2.0 x 10-3 6.9 x 107
a) Determine the order of H2O2 and I– in the
reaction. 4. 1.0 x 10-2 4.0 x 10-3 4.6 x 107

b) Calculate the initial rate coefficient for the 5. 1.0 x 10-2 6.0 x 10-3 6.9 x 107
reaction.
c) Calculate the initial rate for a mixture of the two components where the inital concentration of both is 0.01 M.
d) Estimate the concentration of iodide and peroxide after 1 μs in the reaction in c) supposing that this is an
elementary reaction.
Problem 12 The catalytic decomposition of isopropanol on the surface of a V2O5 catalyst, leading to the products in
the scheme, satisfies a first order kinetic equation. Five seconds after initiation of the reaction at 590 K, the
concentrations of the components in the reaction mixture are:
cA = 28.2 mmol/dm3
cB = 7.8 mmol/dm3
cC = 8.3 mmol/dm3
cD = 1.8 mmol/dm3

a) What is the initial concentration c0 of C3H7OH in the system?

b) What is the value of the overall rate constant k for the process: C3H7OH → products?
c) What is the interval of time (t1/2) in which the concentration of C3H7OH will reach the value c = c0/2?
d) What are the values of rate constants k1, k2, and k3?
e) What are the values of concentrations cB, cC, cD at t1/2?