CHEM1001 Lecture 26 Worksheet

Fuels and Combustion 1. Heat of Combustion of a Model Fuel Combustion refers to a reaction of a fuel with an oxidizer or oxidant. When we think of fuels we most commonly think of organic materials, especially hydrocarbons, and the most common oxidizer for terrestrial applications is oxygen, O2(g). Lets take ethanol as a model fuel, and calculate its enthalpy of combustion exactly using heats of formation, and also approximately using bond enthalpies. (a) First you need to balance the equation for the reaction, whose products are CO2 and H2O (all in the gas phase). C2H5OH(l) + O2(g) CO2(g) + H2O(g).

To calculate how many water molecules will be produced by this combustion reaction, balance the hydrogens. To calculate how many carbon dioxide molecules will be produces, balance the carbons. Finally, work out how many O2 molecules are needed to account for all the O atoms produced in H2Oand CO2. Dont forget to deduct the O already present in ethanol. (b) Calculate the enthalpy of combustion using the formula for enthalpies of formation of the correct number of moles of products and reactants, Hrxn = Hf (products) - Hf (reactants), and the data table below.

(c) Estimate the enthalpy of combustion using average bond enthalpies (shown below). You do this by identifying the number and type of every bond to be broken in order to (hypothetically) fully dissociate or atomise the correct number of moles of ethanol and O2 reactants. The do the same to form all the necessary bonds for the correct number of moles of water and CO2 products.

Suggest reasons why the estimated answer (c) does not agree with the exact calculation (b).

2. Calorific Value of Fuels The calorific value of a fuel describes the heat released per gram of fuel consumed. In the previous problem you calculated the enthalpy of combustion the heat released per mole of ethanol reacting with oxygen. (a) To determine the calorific value of ethanol as a fuel, divide this (molar) enthalpy change by the molecular weight of ethanol. (You need to calculate this.) Express your answer in kJ/g.

This is called the net calorific value or lower heating value, which applies to situations where the water produced is in the vapor state. More heat is released when the products are brought back to the starting temperature (e.g. room temp), so that any water is condensed into a liquid, and this is referred to as the gross calorific value or upper heating value. (b) We can Use Hesss Law to convert net into gross calorific values by simply adding the appropriate enthalpy change. Write out an expression (in the form of a chemical reaction) for the phase transition of water vapour into liquid water.

The enthalpy of vaporization of water is 40.68 kJ/mol, and the enthalpy of fusion of water is 6.02 kJ/mol. What is the value of the enthalpy change for the process expressed above?

Use this to calculate the enthalpy of combustion of ethanol to yield liquid water (balance the equation first). C2H5OH(g) + O2(g) CO2(g) + H2O(l).

Now calculate the gross calorific value for the combustion of ethanol.