Topic 1.

4: Energetics

Summary
a) Enthalpy change (H) The enthalpy (H) of a substance can be considered as kind of chemical energy. When physical or chemical changes occur, the enthalpy of the products is generally not equal to the enthalpy of the reactants and the difference between the two is absorbed or given out in the form of heat energy (q) to the surroundings. The enthalpy change for a process is denoted as H. As a consequence of the Law of Conservation of Energy, the overall energy change must be zero, so H = -q. b) Enthalpy level diagrams The enthalpy of the reactants and products in a chemical reaction can be represented on a H (g) + I (g) diagram in which the vertical position relates to the enthalpy of the system c) Exothermic and endothermic reactions
2 2

If the enthalpy of the products is lower than that of the reactants, H < 0 and q > 0. Heat is Enthalpy -9 (H) given out and we refer to the reaction as exothermic (as shown for the reaction between hydrogen and iodine, right). If H > 0 and q < 0, heat is absorbed and the reaction is 2 HI(g) endothermic. d) Experimental determination of enthalpy change Progress of reaction Definitions of the standard enthalpy change of reaction, formation, combustion, neutralisation and atomisation are given on the definitions sheet for this topic. -3 Standard conditions are: a temperature of 298K, pressure of 1atm and concentrations of 1 mol dm (where applicable) The heat (q) absorbed or given out during a change can be determined by measuring the temperature change induced in a known mass of water. Providing heat loss/gain is minimised (insulation) or compensated for (cooling curve extrapolation) e) Hesss Law In some cases it is not possible to carry out a physicochemical change in a manner in which q can be measured. In such cases, H for the change can be determined by experimentally determining (or looking up) two (or more) values of H for appropriate changes and subsequently applying Hesss Law which states: The enthalpy change for a chemical reaction is independent of the route by which it takes place (provided that the temperatures, pressures and physical states of the reactants and products are the same in each case) f) Evaluating experimental results When a physicochemical change is associated with a change in temperature of the system or its surroundings, the heat change (q) can be determined form the equation: q (in J) = mass (in g) specific heat capacity (in J g K ) temperature change (in K) If the reaction is carried out in dilute aqueous solution (i.e. a large excess of water), the heat absorbed by the reactants/products themselves can be ignored and the values of m, cp and T are those which apply to the water used in the experiment. If the water is contained in a substantial calorimeter (which requires a significant amount of heat to raise its temperature) the apparatus must first be standardised using a reaction for which H is known. For reactions which cannot be carried out directly, it may be possible to use Hesss Law to obtain a value for H, e.g.
-1 -1

H1 (2 HCl + ) CaCO 3 H2 CaCl2 + CO 2 + H 2O CaO + CO 2 ( + 2 HCl) H3 H1 = H2 - H3 H2 and H3 may both be experimentally determined

g) Bond enthalpy is defined as the enthalpy change when one mole of a (certain type of) bond in a gaseous substance undergoes homolytic cleavage. This can only be determined precisely for bonds in gaseous diatomic molecules (e.g. H2, HCl). For all other types of bond, the bond enthalpy will depend on the exact chemical environment and will therefore differ slightly between different molecules (e.g. the C-H bond enthalpy will be different in CH3OH and CH4). In such cases, average bond enthalpies will usually be tabulated in data books which correspond to the average bond enthalpy of a particular type of bond (e.g. C-H) in a variety of different molecules. Average bond enthalpies can be used in Hesss Law calculations, if the alternative route goes via the gaseous atoms resulting from the breaking of all the bonds in the reactants. Chemical bonds with a large bond enthalpy are difficult to break and thus there is generally a high activation energy for -1 reactions in which they must be broken. This explains why nitrogen gas (ENN = 945 kJ mol ) is such an unreactive substance.

11/11/2009