Class work 3, PMY 221

Topic: Thermodynamics
Review: For your calculations take note of the following,
1. Derive equation 2.25 from using definition of heat capacity as given by equation 2.22
then show the integrated form of equation 2.25 as used in example 2.4
2. For an adiabatic process, q = 0, since first law of thermodynamics is ∆U = q + w, ∆U = w
3. For an isothermal process, T = 0, therefore ∆U = 0, since internal energy, a state function
depends on temperature, T, therefore; q = -w
4. Reversible adiabatic expansion of a perfect gas, PfVf ᵞ = PiViᵞ .The value of ᵞ shall be
provided (Boyle’s law) Correction for yesterday. It is not Charles’ law
5. Reversible adiabatic expansion in a thermally insulated container
Tf = Ti (Vi/Vf)1/c.
6. W = Cv∆T, work done during a reversible adiabatic process.
Thermochemistry
The study of energy transferred as heat during the course of chemical reactions. (Read about the
introductory part of thermochemistry from Physical Chemistry by Atkins)
Read and thoroughly understand the following sections in Physical Chemistry by Atkins, and
attempt the following tasks;
- Section 2.7, 2.7 (a) (pay attention to the Born-Haber Cycle, i.e, fig.2.19, and how to
calculate the lattice enthalpy), 2.7(b), 2.7(c), example 2.5.
- Section 2.8, 2.8(a) only.
Tasks
1. From the following data, determine ∆fHᶿ = for diborane, B2H6(g), at 298 K:
i. B2H6(g) + 3 O2 (g) B2O3 (s) + 3 H2O (g) ∆rHᶿ = -2036 kJ mol-1
ii. 2B(s) + 3/2 O2 (g) B2O3 (s) ∆rHᶿ = -1274 kJ mol-1
iii. H2(g) + 1/2 O2 (g) H2O (g) ∆rHᶿ = -241.8 kJ mol-1
[ANS=36.6 kJ]
2. From the following thermodynamic data, determine ∆fHᶿ for DyCl3(s)
i. DyCl3(s) DyCl3(aq) ∆rHᶿ = -180.06 kJ mol-1
ii. Dy(s) + 3 HCl (aq) DyCl3(aq) + 3/2 H2 (g) ∆rHᶿ = -699.43 kJ mol-1
iii. ½ H2(g) + 1/2 Cl2 (g) HCl ∆rHᶿ = -158.31 kJ mol-
[ANS=-994.3 kJ]
 Simple guidelines for manipulating thermochemical equations
- When the question requires you to determine the standard enthalpy of formation of a
substance, i.e, ∆fHᶿ(J) where J is the substance, you must manipulate your
thermochemical equations in such a way that you end up with a net equation which
shows the formation of J only from its elements in their standard states.
- Any thermochemical equation on your data can be reversed depending on the desired net
equation and when a thermochemical equation is reversed, the enthalpy value reverses,
i.e. if the value was a negative one, it reverses to a positive one after reversal and vice
versa.
- When cancelling common substances that appear on both sides of the equation, it could
be necessary to at times multiply a given equation by a certain factor that ensures
cancellation; then the enthalpy value is also multiplied by the same factor
- At times when there are 3J on one side of the equation and 2J on the other side and J
should appear in the final equation, cancellation of J to get the net J required is done by
3J – 2J = J. The J will appear on the side which had J in excess.
3. Read about equation 2.34b do the example in the brief illustration that follows.
4. Calculate the lattice enthalpy strontium iodide, SrI2 from the following data
(Born – Haber cycle)
REACTION ∆H/(kJ mol-1)
Sublimation of Sr (s) +164
Ionization of Sr(g) to Sr2+(g) +1626
Sublimation of I2(s) +62
Dissociation of I2(g) +151
Electron attachment to I (g) -304
Formation of SrI2(s) from Sr(s) and I2(s) -558
Formation of a solid from a gas -∆HL/(kJ mol-1)
[ANS; ∆HL= 1953 kJ mol-1]
5. State Hess’ law of constant heat summation

Ensure you go through all the work given. The recommended book may not be user
friendly to some extent but persistent use will make it user friendly. You are advised to
use other supplementary textbooks to complement your understanding. You must study
this course every day.
Have a good day…..
Assignment one is being prepared…..