Enthalpy

A Quick Guide

Introduction
What is enthalpy?
The energy of a system For example, the energy contained within a compound Given the symbol H

Enthalpy
Chemical reactions that give out energy in the form of heat are known as
exothermic

Chemical reactions that take in energy in the form of heat are known as
endothermic

Enthalpy
In exothermic reactions the products have less energy than the reactants
Reactants Products

Since you cant destroy energy the energy is given out to the surroundings as heat This is known as an
enthalpy change

Measuring Enthalpy
We cant measure how much energy a compound has in it instead we measure the change in energy (H) when it reacts instead H = Hproducts - Hreactants
If H is negative then the reactants give out energy (exothermic)
If H is positive then the reactants take in energy (endothermic)

Measuring Enthalpy
Enthalpy level diagrams chart this change
enthalpy

reactants
Energy given out therefore change in enthalpy is negative

products
Energy taken in therefore change in enthalpy is positive

products

reactants

Units of Enthalpy
Enthalpy is measured in kilojoules per mole (kJ mol-1) For example:
CH4 + 2O2 2H2O + CO2
For every one mole of CH4

(H = -890kJ mol-1)
890kJ of energy is given out

Measuring Enthalpy
The H can vary with conditions We assume our reactions to have taken place at standard conditions:
A specified temperature (25oC / 298K) A standard pressure of 1 atmosphere A standard concentration of 1 mol dm-3

Measuring Enthalpy
Enthalpy can be measured by measuring the transfer of energy to or from water in a bomb calorimeter
Energy transferred = cmT Where:

c = specific heat of water (4.17J g-1 K-1) m = mass of water in grams T = change in temperature of water

Showing Enthalpy Changes

Enthalpy changes must always be accompanied by a chemical equation For example: H2 + O2 H2O (H = -286kJ mol-1)

But
2H2 + O2 2H2O (H = -572kJ mol-1)

Enthalpy
When 1 mole of fuel is burned under standard conditions we get standard enthalpy change of combustion (Hc) Remember the bigger the negative number the more exothermic the more energy given out

Enthalpy
When 1 mole of compound is formed under standard conditions we get standard enthalpy change of formation (Hf) Just because Hc is exothermic doesnt mean that Hf is endothermic 2H2 + O2 2H2O (H = -572kJ mol-1)

Enthalpy Cycles
Since we cant measure the energy given out or taken in when all compound are created we have to use an enthalpy cycle For example:

C + 2H2 CH4

(Hf = -75kJ mol-1)

doesnt happen under normal conditions

Enthalpy Cycles
H cant be measured this way

C + 2H2
H can be measured this way

CH4

CO2 + 2H2O

Theoretically the energy changes that occur in either route are the same Therefore, if we can measure one we will know the other

Enthalpy Cycles
The Universe states that energy cannot be created or destroyed
Law of Conservation of Energy

So, as long as your starting and finishing points are the same the enthalpy change will be the same no matter how you get there

Hesss Law
Hess stated that the sum of enthalpy changes for a series of reaction is the same as the overall enthalpy change So, if you know the enthalpy change in two parts of the cycle, then you can work out the third part of the cycle H1 = H2 H3

Hesss Law
C + 2H2 H 2 H 1 H 3 CO2 + 2H2O CH4

H1 = Hf of 1 mole of methane H2 = Hc of 1 mole of carbon with 2 moles of H2 H3 = Hc of 1 mole of methane

Hesss Law

C + 2H2 H2

H1

CH4 H3

CO2 + 2H2O

H1 = H2 H3 Hf (CH4) = (Hc (C) + 2Hc (H2)) Hc (CH4) Where:

Hc (C) = -393kJ mol-1 Hc (H2) = -286kJ mol-1 Hc (CH4) = -890kJ mol-1

Hesss Law
Hf (CH4) = (Hc (C) + 2Hc (H2)) Hc (CH4) Hf (CH4) = (-393 + (2 x -286)) 890

Hf (CH4) = -75kJ mol-1

Therefore, even though we cant directly measure it, the energy given out when creating methane from carbon and hydrogen is 75kJ mol-1

Hesss Law
The direction of the arrows in the cycle make a difference
NH3 + HCl H 2 H 1 NH4Cl H 3 N2 + 2H2 + Cl2

H1 = -H2 + H3

Hesss Law
NH3 + HCl H2 H 1 NH4Cl H 3 N2 + 2H2 + Cl2

Where: Hf (NH3) = -46.1kJ mol-1 Hf (HCl) = -92.3kJ mol-1 Hf (NH4Cl) = -315kJ mol-1 H1 = -H2 + H3 H2 = Hf (NH3) - Hf (HCl) H3 = Hf (NH4Cl)

Hesss Law
H1 = -(Hf (NH3) - Hf (HCl)) + Hf (NH4Cl) H1 = -(-46.1) (-92.3) + (-315) H1 = -176.6kJ mol-1

Therefore, 176.6 kJ of energy are given out every time one mole of NH4Cl is created

Bond Enthalpy
The energy needed to break a particular bond is called
bond enthalpy

H2 2H

H = +436kJ mol-1

Notice that bond enthalpy is always positive (endothermic) because it requires energy to be put in to break the bond

Bond Enthalpy
These can be worked out using enthalpy cycles
CH4 + 2O2 H 2 H 1 CO2 + H2O H 3 C + 4H + 4O

Using this cycle we can work out the enthalpy change for the combustion of methane (Hc (CH4))

Bond Enthalpy
CH4 + 2O2 H 2 H 1 CO2 + H2O H 3 C + 4H + 4O

H2 = enthalpy change when bonds are broken (4 x C-H bonds) + (2 x O=O bonds) H3 = enthalpy change when bonds are formed (2 x C=O bonds) + (4 x H-O bonds)

Bond Enthalpy
Bond enthalpies: C-H = +413kJ mol-1 O=O = +498kJ mol-1 C=O = +805kJ mol-1 H-O = +464kJ mol-1

H2 = (4 x +413) + (2 x +498)
H3 = -((2 x +805) + (4 x +464))

+2,648kJ mol-1

-3,4466J mol-1

Therefore, overall energy change in burning methane is H2 + H3 or -818kJ mol-1

Important
The reason we get a different answer than before:
Hc (CH4) = -75kJ mol-1 (using reactants and products) Hc (CH4) = -818kJ mol-1 (using bond enthalpies)

is because in bond enthalpies everything has to be in a gaseous state and is therefore no to the standard state used in reactants and products