Tutorial 2-With Answers

Tutorial 2
1. Silylene (SiH2) is a key intermediate in the thermal decomposition of silicon hydrides

such as silane (SiH4) and disilane (Si2H6). If  Ho (SiH2) = +274 kJ mol-1,  Ho (SiH4) =
+34.3 kJ mol-1 and  Ho(Si2H6) = +80.3 kJ mol-1, calculate the standard enthalpies of the
following reactions
(a) Si H4(g) → SiH2(g) + H2(g)
(b) Si2H6(g) → SiH2(g) + SiH4(g)
2. From the following reactions determine  Ho and  Uo for reaction 3

1. H2(g) + Cl2 (g) → 2HCl(g)  Ho = -184.62 kJ mol-1
2. 2H2 (g) + O2 (g) → 2H2O(g)  Ho = - 483.64 kJ mol-1
3. 4HCl(g) + O2 (g) → 2Cl2 (g) + 2H2O (g)
3. For van der Waals gas, T=a/Vm2. Calculate Um for the isothermal expansion of
nitrogen from an initial volume 1.00 dm3 to 24.8 dm3 at 298 K. What are the values of q
and w.
4. The volume of a certain liquid varies with temperature as
V = V’[0.75 + 3.9 x 10-4 (T/K) + 1.48 x 10-6 (T/K)2
Where V’ is the volume at 300 K. Calculate its expansion coefficient, , at 310 K. Give
your comment on the answer.
5. Given that  = 0.25 K atm-1 for nitrogen, calculate the value of its isothermal Joule-
Thomson coefficient. Calculate the energy that must be supplied as heat to maintain
constant temperature when 15.0 mol N2 flows through a throttle in an isothermal Joule-
Thomson experiment and the pressure drop is 75 atm.
6. A sample consisting of 1 mol of perfect gas atoms is taken through the cycle shown in
the Figure below.
(a) Determine the temperature at the points 1, 2, and 3.
(b) Calculate q, w, ΔU, and ΔH for each step and for the overall cycle. If a numerical
answer cannot be obtained from the information given, then write +, −, 0, or ? as
appropriate
7. A sample of 1.00 mol perfect diatomic gas molecules is put through the following
cycle: (a) constant-volume heating to twice its initial pressure, (b) reversible, adiabatic
expansion back to its initial temperature, (c) reversible isothermal compression back
to its initial pressure. Calculate q, w, ΔU, and ΔH for each step and overall. (Initial
condition 298 K, 1.00 atm).
8. The molar heat capacity of ethane is represented in the temperature range 298 K to
400 K by the empirical expression Cp,m /(J K-1mol-1) = 14.73 + 0.1272(T/K). The
corresponding expressions for C(s) and H2(g) are given in Table 2.2 (Atkins). Calculate
the standard enthalpy of formation of ethane at 350 K from its value at 298 K.
9. The standard enthalpy of formation of the metallocene bis(benzene)chromium was
measured in a calorimeter. It was found for the reaction
Cr(C6H6)2(s) → Cr(s) + 2 C6H6 (g) rUo = 583 kJ mol-1
Find the corresponding reaction enthalpy and estimate the standard enthalpy of
formation of the compound at 583 K. The constant-pressure molar heat capacity of
benzene is 136.1 J K-1 mol-1 in its liquid range and 81.67 J K-1 mol-1as a gas.
10. When 1.3584 g of sodium acetate trihydrate was mixed into 100.0 cm3 of 0.2000 M
HCl(aq) at 25°C in a solution calorimeter, its temperature fell by 0.397°C on account of
the reaction:
H3O+ (aq) + NaCH3CO2·3H2O(s) → Na+ (aq) + CH3COOH(aq) +4 H2O(l)
The heat capacity of the calorimeter is 91.0 J K-1 and the heat capacity density of the
acid solution is 4.144 J K-1 cm-3. Determine the standard enthalpy of formation of the
aqueous sodium cation. The standard enthalpy of formation of sodium acetate
trihydrate is −1604 kJ mol-1.
11. A fluorocarbon gas was allowed to expand reversibly and adiabatically to twice its
volume; as a result, the temperature fell from 298.15 K to 248.44 K and its pressure
fell from 202.94 kPa to 81.840 kPa. Evaluate Cp.
12. Calculate the work done during the isothermal reversible expansion of a gas that
satisfies the virial equation of state. Evaluate (a) the work for 1.0 mol Ar at 273 K
(second virial coefficient -21.7 cm3 mol-1) and (b) the same amount of a perfect gas.
Let the expansion be from 500 cm3 to 1000 cm3 in each case.
13. Calculate the difference in molar entropy (a) between liquid water and ice at –5°C, (b)
between liquid water and its vapour at 95°C and 1.00 atm. The differences in heat
capacities on melting and on vaporization are 37.3 J K-1 mol-1 and –41.9 J K-1 mol-1,
respectively. Distinguish between the entropy changes of the sample, the
surroundings, and the total system, and discuss the spontaneity of the transitions at
the two temperatures.
14. A Carnot cycle uses 1.00 mol of a monatomic perfect gas as the working substance
from an initial state of 10.0 atm and 600 K. It expands isothermally to a pressure of
1.00 atm (Step 1), and then adiabatically to a temperature of 300 K (Step 2). This
expansion is followed by an isothermal compression (Step 3), and then an adiabatic
compression (Step 4) back to the initial state. Determine the values of q, w, ΔU, ΔH,
ΔS, ΔStot, and ΔG for each stage of the cycle and for the cycle as a whole.

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Tutorial 2

1. Silylene (SiH2) is a key intermediate in the thermal decomposition of silicon hydrides

2. From the following reactions determine  Ho and  Uo for reaction 3

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