Hess Law

Starter: Why is it easy to measure enthalpies of combustion but often difficult to measure enthalpies of formation?

Problem
How would you measure the enthalpy change for the formation of methane from graphite and hydrogen gas?
problem: graphite doesnt react with hydrogen gas to form methane
C(graphite) + 2H2(g) CH4(g)

Hesss Law

Start

Finish

Both lines accomplished the same result, they went from start to finish. Net result = same.

Hesss Law
When reactants are converted to products, the change in enthalpy is the same whether the reaction takes place in one step or a series of steps.

Remember
P4(s) + 3O2(g) P4O6(s) H = -1640.1 kJ

Transform the equation so that P4O6(s) is on the reactant side. P4O6(s) P4(s) + 3O2(g) -H = 1640.1 kJ

Note: if the equation switches, the sign of H does as well.

Example
What is the change in enthalpy for the formation of methane from graphite and hydrogen gas?
problem: graphite doesnt react with hydrogen gas to form methane
C(graphite) + 2H2(g) CH4(g)

Solution
Find reactions that do occur that link graphite to methane through a series of steps.

Enthalpy of reaction from enthalpies of formation

If you formed the products from their elements you should need the same amounts of every substance as if you formed the reactants from their elements.

Enthalpy of formation tends to be an exothermic process

Enthalpy of reaction from bond enthalpies

Calculate the enthalpy change for the hydrogenation of ethene

Enthalpy of reaction from bond enthalpies

Calculate the enthalpy change for the hydrogenation of ethene

DH2

1 x C=C bond 4 x C-H bonds 1 x H-H bond

@ 611 @ 413 @ 436

= 611 kJ = 1652 kJ = 436 kJ = 2699 kJ

Total energy to break bonds of reactants

Enthalpy of reaction from bond enthalpies

Calculate the enthalpy change for the hydrogenation of ethene

DH2

1 x C=C bond 4 x C-H bonds 1 x H-H bond

@ 611 @ 413 @ 436

= 611 kJ = 1652 kJ = 436 kJ = 2699 kJ = 346 kJ = 2478 kJ = 2824 kJ = (2699 2824) = 125 kJ

Total energy to break bonds of reactants DH3 1 x C-C bond 6 x C-H bonds @ 346 @ 413

Total energy to break bonds of products Applying Hesss Law

DH1 = DH2 DH3

Enthalpy of reaction from enthalpies of formation

Sample calculation Calculate the standard enthalpy change for the following reaction, given that the standard enthalpies of formation of water, nitrogen dioxide and nitric acid are -286, +33 and -173 kJ mol-1 respectively; the value for oxygen is ZERO as it is an element

2H2O(l)

4NO2(g)

O2(g)

>

4HNO3(l)

DH = DHf of products DHf of reactants

By applying Hesss Law ... The Standard Enthalpy of Reaction DHr will be... PRODUCTS [ 4 x DHf of HNO3 ] minus DHr = 4 x (-173) REACTANTS [ (2 x DHf of H2O) + (4 x DHf of NO2) + (1 x DHf of O2) ] 2 x (-286) ANSWER = - 252 kJ + 4 x (+33) + 0

Enthalpy of reaction from enthalpies of combustion

If you burned all the products you should get the same amounts of oxidation products such a CO2 and H2O as if you burned the reactants.

Enthalpy of combustion is an exothermic process

Enthalpy of reaction from enthalpies of combustion

Sample calculation Calculate the standard enthalpy of formation of methane; the standard enthalpies of combustion of carbon, hydrogen and methane are -394, -286 and -890 kJ mol-1 . C(graphite) + 2H2(g) > CH4(g)

DH = DHc of reactants DHc of products

By applying Hesss Law ... The Standard Enthalpy of Reaction DHr will be... REACTANTS [ (1 x DHc of C) + (2 x DHc of H2) ] DHr = 1 x (-394) + 2 x (-286) minus PRODUCTS [ 1 x DHc of CH4] 1 x (-890)

ANSWER = - 76 kJ mol-1

Determine the heat of reaction for the reaction:

4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
Using the following sets of reactions: N2(g) + O2(g) 2NO(g) N2(g) + 3H2(g) 2NH3(g) 2H2(g) + O2(g) 2H2O(g) DH = 180.6 kJ DH = -91.8 kJ DH = -483.7 kJ

Determine the heat of reaction for the reaction: C2H4(g) + H2(g) C2H6(g) Use the following reactions: C2H4(g) + 3O2(g) 2CO2(g) + 2H2O(l) C2H6(g) + 3.5 O2(g) 2CO2(g) + 3H2O(l) H2(g) + 0.5 O2(g) H2O(l) DH = -1401 kJ DH = -1550 kJ DH = -286 kJ

Consult your neighbor if necessary.