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Energetics
Extreme cases:
- The enthalpy of neutralisation of HF acid by NaOH is – 68.6 kJmol-1 although HF is
a weak acid. The dissociation of HF produces a small fluoride (F–) ion with a large
hydration energy. The large hydration energy dominates other factors put together.
F–(g) + aq → F–(aq);H = -506 kJmol–1.
- The enthalpy of neutralisation of HCN acid by NH3 is – 5.4 kJmol-1 because HCN is
a very weak acid and NH3 a weak base. Much energy is absorbed to dissociate HCN
and NH3 as neutralisation proceeds.
i. Standard enthalpy of solution (H ).
This is the enthalpy change when one mole of a solute is completely dissolved to form an
infinitely dilute solution under standard conditions (1atm and 298K).
NaCl(s) + aq → NaCl(aq); H NaCl(s)
ii. Standard enthalpy of dilution (H ).
This is the enthalpy change when a molar solution is diluted in a large volume of solvent
such that further dilution causes no further enthalpy change under standard conditions
(1atm and 298K).
NaCl(aq) + aq → NaCl(aq); H NaCl(aq)
iii. Standard enthalpy of Hydration enthalpy
The enthalpy change when one mole of gaseous ions is completely hydrated in water under
standard conditions (298K and 1 atm).
Na+(g) + aq → Na+(aq); H Na+(g) = - 406kJmol-1.
Cl-(g) + aq → Cl-(aq); H Cl-(g) = - 377kJmol-1.
Act:
(a) A neutralisation reaction between H2SO4 acid and NaOH when appropriate volumes of their
respective solutions are mixed.
(i) Write a balanced equation for the neutralisation reaction between the acid and base.
(ii) Would you expect the equation you have written in (a) (i) above to represent standard
enthalpy change of neutralisation between the acid and base? Explain.
(b) What does the term infinitely dilute solution in the definition of standard enthalpy change of
solution mean?
7.6 Determination of Enthalpy Changes
i) Determination of standard enthalpy of solution.
th er m o m eter
li d Procedure:
expa n d ed
A known volume of distilled
p o l yst yr e n e c u p
water is placed in a polystyrene
bea ker
cup and placed in a beaker with
cotton wool for insulation.
So l u t i o n Initial temperature of the water
is recorded. A known mass of a
co tto n soluble compound is then added
wo o l to the polystyrene cup and
stirred with a thermometer until
there is no further change in temperature. The maximum or minimum temperature of the
solution is recorded. The heat change (∆q) between the system and the surroundings is
calculated using the expression (∆q) = mc∆T, where m = mass of water or mixture, c =
specific heat capacity of water and ∆T = temperature change.
Assumptions:
THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N
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Energetics
o Heat change on mixing is absorbed only by water and calorimeter
o Specific heat capacity of the solution is equal that of water; i.e. 4.18Jg-1k-1.
o Density of solution equals to density of water at 4°C i.e. 1g/cm3.
From the last assumption, the volume of water or mixture used for the experiment is always
taken as the mass of water or mass of mixture.
Act:
In one such experiment, the following data was collected after adding 4.0g of sodium
hydroxide (NaOH) to 100 cm3 of water.
- Initial temperature of water = 25.0°C, Maximum temperature of solution = 35.0°C.
(a) Calculate the heat change (∆q) between the system and the surroundings.
(b) Calculate the number of moles of NaOH used for the experiment
(c) Calculate the standard enthalpy change of solution of NaOH including a sign.
Note:
The enthalpy change of a solution of a compound can be exothermic if a rise in temp is
noticed during the dissolving or mixing process.
the enthalpy change of a solution of a compound can be endothermic if a fall in temp is
noticed during the dissolving or mixing process.
ii) Determination of enthalpy of combustion of liquid alkanes and alcohols.
Thermometer Procedure:
Calorimeter A spirit burner is filled with liquid fuel (alkane
Water or alcohol, weighed and its mass recorded.
Flame A known volume or mass of water in a copper
Wick Draught Shield can calorimeter is placed just above the spirit
Spirit burner burner. The initial temperature of the water is
Ethanol measured and recorded.
The spirit burner is then lit to warm the water. When an appreciable rise in temperature is
noted, the flame is put off and the spirit burner reweighed immediately.
A bomb calorimeter is a more accurate set-up for measuring enthalpies of combustion and
can be used to measure enthalpies of combustion of a substance in any state of matter.
Act:
In one such experiment on ethanol, the following data was collected.
Mass of copper can calorimeter and water = 394.89g.
Mass of copper can calorimeter alone = 294.89g.
Mass of spirit burner and its content before burning = 55.23g.
Mass of spirit burner and its content after burning = 54.08g.
Initial temperature of water = 25.0°C.
Maximum temperature of solution = 27.7°C.
(a) Calculate the mass of water used for the experiment.
(b) Calculate the mass of ethanol burnt during the experiment.
(c) Calculate the heat change (∆q) transferred to water assuming no heat absorbed by the
calorimeter. Specific heat capacity of water (c) = 4.18 Jg–1K–1.
(d) Calculate the heat change (∆q) transferred assuming that all heat produced is absorbed
by calorimeter and water only. Specific heat capacity of copper (c) = 2.10 Jg–1K–1.
(e) Calculate the number of moles of ethanol burnt during the experiment
(c) Calculate the standard enthalpy change of combustion of ethanol including a sign.
Assumptions:
- Heat produced by burning the substance is only absorbed by water and calorimeter
- Density of water is 1gcm-3.
THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N
