IAS Chemistry Ms.
Pabasari Goonetilleke
Unit 2 BSc. MSc. Chemistry
Energetics
Energetics
Chemical energy is made up of two components;
- kinetic energy - Measure of motion of the particles (atoms, molecules or ions) in a substance
- potential energy - Measure of how strongly these particles interact with one another (attract and
repel)
Heat and Temperature
Heat Temperature
Enthalpy
………………………………………………………………………………………………..
Cannot be measured directly
Enthalpy change (H)
• The heat energy transferred between the system and the surroundings provided the pressure is constant
• The standard conditions are 100 kPa and a specified temperature, usually 298 K
• When an enthalpy change is measured at standard conditions the symbol is used
Exothermic and endothermic reactions
Exothermic change Endothermic change
Examples: Examples:
combustion of fuels Thermal decomposition of calcium carbonate
Freezing water Melting ice
Dissolving NaOH in water Dissolving Ammonium nitrate in water
oxidation of carbohydrates such as glucose in Photosynthesis
respiration
Question Draw enthalpy change diagrams for the following reactions
C(s) + O2(g) CO2 (g) H =-394kJmol-1 C(s) + CO2(g) 2CO (g) H =+172kJmol-1
Standard enthalpy change of reaction (rH)
…………………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………………
(It is the enthalpy change when the number of moles of reactants as specified in the balanced equation react
together)
For the reaction,
N2(g) + 3H2(g) 2NH3(g) rH =-92kJmol-1
But for the reaction when written as
½ N2(g) + 1 ½ H2(g) NH3(g) rH =-46kJmol-1
In each case, ‘per mole’refers to one mole of equation and not to one mole of any reactant or product
Standard enthalpy change of formation (fH)
…………………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………………
Examples:
The enthalpy of formation of an element is 0 kJ mol-1
Standard enthalpy change of combustion (cH)
…………………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………………
Examples:
Incomplete combustion will lead to soot (carbon), carbon monoxide and water. It will be less exothermic than
complete combustion.
Enthalpy changes of combustion are always exothermic.
Experimental determination of enthalpy change of combustion of a liquid
- A spirit burner containing the liquid to be tested (eg: methanol)
is weighed
- A known volume of water is measured
- The initial temperature of the water is measured
- The burner is lit
- The mixture is constantly stirred with the thermometer
- When the temperature of the water is increased by 20oC the
flame is extinguished and the burner is immediately reweighed
- The final temperature is measured
Errors in the method
- energy transfer from surroundings (usually loss)
- Some of heat energy produced may transfer to the copper can
- Some of the fuel may not burn completely
- The conditions are not standard
- Experiment takes a long time
Steps in calculating Enthalpy Change
Examples
1. Use the given information to find the enthalpy change
Volume of water heated 100.0 cm3
Mass of ethanol burned 0.420 g
Temperature change (T) 24.5 oC
2. Calculate the enthalpy change of combustion for the reaction where 0.65g of propan-1-ol was completely
combusted and used to heat up 150g of water from 20.1 to 45.5oC
Enthalpy change of neutralization (neutH)
…………………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………………
Examples:
Enthalpy changes of neutralisation are always exothermic.
Experimental determination of enthalpy change of neutralization
- Measure out desired volumes of solutions with volumetric pipettes and transfer
the acid to the insulated cup
- Measure the initial temperatures of the acid and alkali separately
- Add the alkali to the polystyrene cup
- Stir the mixture
- Record the maximum temperature
If the reaction is slow then the exact temperature rise can be difficult to obtain as cooling occurs
simultaneously with the reaction
The method can be modified as follows
- Measure out desired volumes of solutions with
volumetric pipettes and transfer to insulated cup
- Measure the initial temperatures of the solution (or
both solutions if 2 are used) Do this every minute
for 2-3 minutes
- At minute 3 transfer second reagent to cup. If a solid
reagent is used then add the solution to the cup
first and then add the solid weighed out on a
balance (If using a solid reagent then use ‘before
and after’ weighing method)
- Stir the mixture (ensures that all of the solution is at
the same temperature)
- Record temperature every minute after addition and record the maximum temperature
- Plot the readings
Errors in the method
- energy transfer from surroundings (usually loss)
- approximation in specific heat capacity of solution. The method assumes all solutions have the heat
capacity of water
- neglecting the specific heat capacity of the calorimeter- we ignore any energy absorbed by the apparatus
- reaction or dissolving may be incomplete or slow
- Density of solution is taken to be the same as water
Examples
1. Use the given information to find the enthalpy change of neutralisation of the reaction between HCl and
NaOH
Volume of 1.00moldm-3 HCl 25.0 cm3
Volume of 1.2moldm-3 NaOH 25.0 cm3
Initial temperature of acid 18.6 oC
Initial temperature of alkali 18.8 oC
Maximum temperature reached 25.4 oC (298.5K)
2. Calculate the enthalpy change of reaction for the reaction where 25cm3 of 0.2 M copper sulfate was reacted
with 0.01mol (excess of zinc). The temperature increased was7oC
3. 25cm3 of 2M HCl was neutralised by 25cm3 of 2M NaOH. The temperature was increased by 13.5oC.
Calculate the enthalpy change per mole of HCl?
Enthalpy change of atomisation (atH)
…………………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………………
Examples:
• Some standard enthalpy changes of formation cannot be determined experimentally
Example:
• It is impossible to make only carbon monoxide by burning carbon with oxygen
• However, the following enthalpy changes can be used to determine the standard enthalpy change of
formation of carbon monoxide
Flip Equation B and add to equation A
enthalpy change of
formation of carbon
monoxide
Examples:
Calculate the enthalpy change of the following reaction using the given equations.
1. 2S + 3O2 → 2SO3 ∆H =?
(A) S + O2→ SO2 ∆H = - 297 kJ/mol
(B) 2SO3 → 2SO2 + O2 ∆H = 198 kJ /mol
2. Sn + 2Cl2 → SnCl4
Sn + Cl2 → SnCl2 ∆H = -325 kJ /mol
SnCl2 + Cl2 → SnCl4 ∆H = -186 kJ /mol
3. C2H4 (g) + H2 (g) → C2H6 (g).
C2H4 (g) + 3 O2 (g) --> 2 CO2 (g) + 2 H2O (l) H = -1411. kJ
C2H6 (g) + 3½ O2 (g) --> 2 CO2 (g) + 3 H2O (l) H = -1560. kJ
H2 (g) + ½ O2 (g) --> H2O (l) H = -285.8 kJ
4. 4 NH3 (g) + 5 O2 (g) --> 4 NO (g) + 6 H2O (g)
N2 (g) + O2 (g) --> 2 NO (g) H = -180.5 kJ
N2 (g) + 3 H2 (g) --> 2 NH3 (g) H = -91.8 kJ
2 H2 (g) + O2 (g) --> 2 H2O (g) H = -483.6 kJ
