Topic 1.

4 Energetics Summary
1.4a Enthalpy * demonstrate an understanding of the term enthalpy change, H

Enthalpy (H) is the heat content of a system. In a reaction this may increase or decrease and produce an enthalpy change (/\H). /\H = H2 - H1 where H1 = enthalpy of reactants and H2 = enthalpy of products The enthalpy change is affected by pressure and temperature so standard conditions are used for measurements. These conditions are 1 atmosphere pressure and a temperature of 25oC or 298K. for 2H2(g) + O2(g) -----> 2H2O(l) standard enthalpy of reaction /\Ho 298 = -571.6 kJmol1

This enthalpy change is per mole of equation. What is the heat change if 1 mol of O2 reacts with hydrogen -571.6 kJmol-1 1 mol of H2 reacts with oxygen = -285.8 kJmol-1 4 mol of H2O are formed from H2 and O2? -1143 kJmol-1
1.4b Enthalpy level diagrams * construct simple enthalpy level diagrams showing the enthalpy change

Exothermic reaction enthalpy level diagram reactants

|

Endothermic reaction enthalpy level diagram products /\ | | reactants | positive enthalpy change

| negative enthalpy change | products \/

A reaction profile shows how the enthalpy of a system changes during the reaction. It shows that heat needs to be put into a system before molecules can react or break up. For example hydrogen and iodine react in a reversible reaction to form hydrogen iodide. H2(g) + I2(g) ---> 2HI(g) (exothermic) The reaction profile is shown below.

Task 1.4b: Draw enthalpy level diagrams and reaction profiles for the reactions shown below: 2H2(g) + O2(g) -----> 2H2O(l) ; /\Ho 298 = -571.6 kJmol-1 2Ag2O(s) ---> 4Ag(s) + O2(g) ; /\Ho 298 = + 61 kJmol-1 C(s) + 2S(s) -----> CS2(l) /\Ho298 = + 88kJmol-1 C3H6 (g) + 4 1/2 O2(g) ----> 3CO2 (g) + 3H2 O (l) /\Ho298 = -2219.7 kJ per mole

1.4c Exothermic and endothermic reactions * recall the sign of H for exothermic and endothermic reactions, eg illustrated by the use of exo- and endothermic reactions in hot and cold packs

An exothermic reaction is one in which heat is given out. It results in a temperature increase. /\H is given a negative sign to indicate an exothermic reaction, e.g. 2H2(g) + O2(g) -----> 2H2O(l) ; /\Ho 298 = -571.6 kJmol-1 An endothermic reaction is one in which heat is taken in. It results in a temperature decrease. /\H is given a positive sign to indicate an endothermic reaction, e.g. 2Ag2O(s) ---> 4Ag(s) + O2(g) ; /\Ho 298 = + 61 kJmol-1
Heat and cold packs are applications of these changes (Active book p35) 1.4d Standard enthalpy changes * recall the definition of standard enthalpy changes of reaction, formation, combustion, neutralization and atomization and use experimental data to calculate energy transferred in a reaction and hence the enthalpy change of the reaction. This will be limited to experiments where substances are mixed in an

insulated container, and combustion experiments

Enthalpy of formation (/\Hof)is the enthalpy change when 1 mole of a substance is formed from its constituent elements in their standard states with measurements made under standard conditions of 298K and 1 atm. C(s) + 2S(s) -----> CS2(l) /\Hof = + 88kJmol-1 The positive sign means that for each mole of CS2 formed 88kJ are absorbed. NB. The enthalpy of formation of an element is O kJmol-1 Enthalpy of combustion (/\Hoc) is the enthalpy change when 1 mole of a substance is burnt completely in oxygen with measurements made at 298K and at 1 atm. C3H6 (g) + 4 1/2 O2(g) ----> 3CO2 (g) + 3H2 O (l) /\Hoc = -2219.7 kJ per mole The negative sign means that each mole of propane burnt releases 2219.7 kJ. Enthalpy of neutralisation (/\Honeut) is the enthalpy change when 1 mol of water is formed by the neutralisation of hydrogen ions by hydroxide ions with measurements made under standard conditions. H+(aq) + OH-(aq) ---> H2O(l) (/\Honeut) = -57kJmol-1 The enthalpy of atomisation is often needed. This is the enthalpy change when 1 mole of gaseous atoms are formed from an element in its standard state. e.g. The enthalpies of atomisation of carbon and hydrogen are the enthalpy changes for: C(s) --> C(g) and 1/2 H2(g) --> H(g) Task 1.4d.1: State the names of the following enthalpy changes and give the amounts of reactant or product that they involve. HCl(aq) + NaOH(aq) ---> NaCl(aq) + H2O(l) C(s) + 2H2(g) ---> CH4(g) C2H5OH(l) + 3O2(g) ---> 2CO2(g) + 3H2O(l) Na(s) Na(g) Task 1.4d.2: Write balanced equations for reactions which would have the following enthalpy changes: Enthalpy of combustion of methane, enthalpy of formation of water, enthalpy of combustion of hydrogen and twice the enthalpy of formation of hydrogen sulfide (H2S), enthalpy of atomisation of chlorine.

1.4e Hesss Law e recall Hesss Law and apply it to calculating enthalpy changes of reaction from data provided, selected from a table of data or obtained from experiments and understand why standard data is necessary to carry out calculations of this type

This states that the total enthalpy change for a chemical reaction is the same regardless of the route taken for the reaction. It is also a consequence of a more general physical law- the Law of Conservation of Energy which states that energy can not be created nor destroyed. route A reactants ----/\H1----> products | /\ /\H2 | | | route B \/ | intermediates -----/\H3---------> Enthalpy change along route A (/\H1) = Enthalpy change along route B (/\H2 + /\H3) /\H1 = /\H2 + /\H3 Applying Hess's Law using enthalpy of formation data

H[reaction] = sum Hfo[products] - sum Hfo[reactants] Task 1.4e.1 Applying Hess's Law using enthalpy of combustion data

H[reaction] = sum Hcomo[reactants] - sum Hcomo[products]

Task 2.1f.2
1.4f Enthalpy Changes from experiment f evaluate the results obtained from experiments using the expression: energy transferred in joules = mass x specific heat capacity x temperature change and comment on sources of error and assumptions made in the experiments. The following types of experiments should be performed: i experiments in which substances are mixed in an insulated container and the temperature rise measured ii simple enthalpy of combustion experiments using, eg a series of alcohols in a spirit burner iii plan and carry out an experiment where the enthalpy change cannot be measured directly, eg the enthalpy change for the decomposition of calcium carbonate using the enthalpy changes of reaction of calcium carbonate and calcium oxide with hydrochloric acid g demonstrate an understanding of the terms bond enthalpy and mean bond enthalpy, and use bond enthalpies in Hess cycle calculations and recognise their limitations. Understand that bond enthalpy data gives some indication about which bond will break first in a reaction, how easy or difficult it is and therefore how rapidly a reaction will take place at room temperature.

Bond dissociation enthalpy is the enthalpy change when one mole of bonds of a particular type in a particular environment are broken. The Bond Enthalpy Term or E is an average value of bond dissociation enthalpies for a particular bond. The bond dissociation enthalpies for the O-H bonds in water differ slightly, the bond enthalpy term is the average. so E(O-H) = Average bond dissociation enthalpy = (494 + 430)/2 kJmol-1 so E(O-H) = +462 kJmol-1 The enthalpy of atomisation is often needed. This is the enthalpy change when 1 mole of gaseous atoms are formed from an element in its standard state. e.g. The enthalpies of atomisation of carbon and hydrogen are the enthalpy changes for: C(s) --> C(g) and 1/2 H2(g) --> H(g) These quantities can be combined to calculate enthalpies of reaction when all of the reactants and products are in the gas state E.g. What is the enthalpy of reaction for the formation of gaseous water given E(O-H) = +462 kJmol-1, E(H-H) = +436 kJmol-1 ,

E(O=O) = 498 kJmol-1 .

Hr + 2E[O-H] = E[H-H] +1/2E [O=O] Hr = E[H-H] +1/2E [O=O] - 2E[O-H] Hr = 436kJmol-1 +1/2*498kJmol-1 -2*462kJmol-1 Hr = -239kJmol-1

H[reaction] = sum [reactants] - sum [products] Task 2.1h