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2.1 - Energy changes


Thermochemistry study of energy changes during chemical reactions - helps measure energy changes in chemical reactions and to explain stability of compounds - allows chemists to decide whether or not a reaction will occur System material/mixture of chemicals being studied Surroundings everything around the system Closed system- no matter can exchange to the surroundings / still energy change Open system energy and matter can exchange

2.2 - Enthalpy change


Is the overall energy exchanged with the surroundings when a change happens at constant pressure and the final temperature is the same as the starting temperature. Enthalpy change - H - kJ mol-1 Exothermic energy leaves system and is given out to surroundings e.g. respiration / burning Endothermic energy taken in from surroundings melting / vaporisation / photosynthesis Products have less energy than reactants in exothermic / more in endothermic

2.3 - Measuring enthalpy changes


Heat given out / taken in can be used to determine enthalpy changes Enthalpy changes from burning fuels From mass of water and its temperature change the amount of heat lost and produced can be measured From the loss of mass in liquid burner, we can find out the mass of fuel which has burned Calculate the heat produced when one 1g of fuel burns Energy transferred (kJmol-1) = mass x specific heat capacity x change in temperature (K) Heat produced when 1 mol of substance burns = molar mass x energy transferred Specific heat capacity of a material is the energy needed to raise the temperature of 1g of material by 1K. (water c = 4.2Jg-1 K-1) Sources of error loss of heat, flame disturbance, incomplete combustion Bomb calorimeter electrical calibration for heat loss / excess oxygen for complete combustion apparatus designed so sample burns completely / heat loss avoided (fuel/food) Adam Clarke www.brain-freeze.co.uk

2 Enthalpy changes in solution insulated plastic containers e.g. polystyrene cups insulator / negligible specific heat capacity exothermic reaction energy released cant escape solution heats up endothermic reaction energy cant enter from surroundings solution cools down enthalpy changes can be recorded from temperature changes assume SHC to be = water 1 find amount in moles 2 - calculate energy transfer 3 divide energy transfer by moles 4 decide whether it is a positive or negative value and apply sign

2.4 Standard enthalpy changes


Standard enthalpy change of a reaction energy transferred when the molar quantities of reactants as stated in the equation react under standard conditions. Standard conditions pressure of 1 atmosphere temperature of 298K stable state concentration of 1mol dm-3 for solution Standard enthalpy change of neutralisation is the enthalpy change when the amounts of acid and alkali in the equation for the reaction neutralise each other under standard conditions. 1 calculate amounts in dm and multiply by number of moles 2 calculate energy transfer 3 divide energy transfer by number of moles Standard enthalpy change of combustion enthalpy change when one mole of the substance burns completely in oxygen under standard conditions. can write using enthalpy change alongside equation or by summarising values are always negative as combustion is exothermic Standard enthalpy change of formation the enthalpy change when one mole of the compound forms from its elements under standard conditions with the elements and the compound in their standard (stable) states. can write using enthalpy change alongside equation or by summarising some are more difficult to measure C,H,O to ethanol have to use indirect method standard enthalpy change of formation for an element = 0 kJ mol-1 no change as it forms from itself Standard enthalpy change of atomisation the enthalpy change when one mole of gaseous atoms is formed from the element under standard conditions molecules to single atoms takes energy

Adam Clarke www.brain-freeze.co.uk

2.5 Hesss law and the indirect determination of enthalpy changes


Hesss Law enthalpy change in converting reactants to products is the same regardless of the route taken i.e. the number of steps used (provided the initial and final conditions are the same). It can be used for: standard enthalpy changes of formation from standard enthalpy changes of combustion (calculate standard enthalpies of formation for substances which cannot be measured directly). standard enthalpy changes of reaction from standard enthalpy changes of formation

Enthalpies of formation from enthalpies of combustion

Constituent Elements

H1 = Hf [compound] Compound

+O2

+O2

H2 = Hc [elements]

H3 = Hc [compound]

Combustion products (CO2 + H20)

H1 = Hf [compound]

H2 = Hc [elements]

H3 = Hc [compound]

Enthalpies of reaction from enthalpies of formation

Hreaction
Reactants Products

H1 = Hf [reactants]
Elements

H2 = Hf [products]

Hreaction

H2 = Hf [products]

H1 = Hf [reactants]

Adam Clarke www.brain-freeze.co.uk

2.6 Enthalpy changes and the direction of change


exothermic reactions tend to occur readily change happens in direction energy spreads H is a guide to the likely direction of change direction of change may depend on the conditions of temperature and pressure some endothermic reaction can occur readily reactions for H can just happen some exothermic reactions never occur because the rate of reaction is so slow

2.7 Enthalpy changes and bonding


bond breaking is endothermic bond making is exothermic The bond enthalpy of a particular bond is the energy required to break one mole of the bonds in a substance in the gaseous state. The enthalpy change of a reaction is the energy difference between bond-breaking and bond-making processes. Bond enthalpy definite quantity of energy associated with each bond Average bond enthalpy average values for one kind of bond in different compounds bond enthalpy for a specific covalent bond varies slightly from one compound to another successive bond enthalpies are not the same in compounds such as water and methane Using bond enthalpies the most important use of mean bond enthalpies is in estimating the enthalpy changes in chemical reactions involving molecular substances with covalent bonds. These estimates are particularly helpful when experimental measurements cant be made.

Hreaction kJ mol-1

H bonds broken

H bonds formed

The values of H estimated from mean bond enthalpies agree closely with experimental values, though there are limitations with using bond energy data like this, because of significant differences between the values of H estimated from bond enthalpies and those obtained by experiment do occur: variations in the strength of one kind of bond in different molecules and mean bond enthalpies should not be used when one of the reactants or products is not in the gaseous state as bond enthalpy calculations assume

Adam Clarke www.brain-freeze.co.uk