Hess' Law (OCR AS Chemistry A) : Revision Note

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Hess’ Law & Enthalpy Cycles

  • Hess’s Law states that:

"The total enthalpy change in a chemical reaction is independent of the route by which the chemical reaction takes place as long as the initial and final conditions are the same."

  • This means that whether the reaction takes place in one or two steps, the total enthalpy change of the reaction will still be the same

Chemical Energetics Hess Cycles, downloadable AS & A Level Chemistry revision notes

According to Hess’ Law, the enthalpy change of the direct route, going from reactants (A+B) to product (C), is equal to the enthalpy change of the indirect routes

Examiner Tips and Tricks

You do not need to learn Hess's Law word for word as it is not a syllabus requirement, but you do need to understand the principle as it provides the foundation for all the problem solving in Chemical Energetics

  • Hess’ Law is used to calculate enthalpy changes which can’t be found experimentally using calorimetry, e.g.:

3C (s) + 4H2 (g) → C3H8(g)

  • ΔfH (propane) can’t be found experimentally as hydrogen and carbon don’t react under standard conditions

Calculating ΔHr from ΔHf using Hess’s Law energy cycles

  • You can see the relationships on the following diagram:

    Chemical Energetics Direct and Indirect Routes, downloadable AS & A Level Chemistry revision notes

The enthalpy change from elements to products (direct route) is equal to the enthalpy change of elements forming reactants and then products (indirect route)

  • The products can be formed:

    • Directly from the elements = ΔH2
      OR
      Indirectly from the elements = ΔH1 + ΔHr

  • Equation

ΔH2 = ΔH1 + ΔHr

  • Therefore for energy to be conserved,

ΔHr = ΔH2 – ΔH1

Examiner Tips and Tricks

There are two rules that you can use to help with your calculations using enthalpy changes of formation and combustion

  • Using enthalpy changes of formation, ΔHf

    • ΔrH = ∑ΔHf(products) - ∑ΔHf(reactants)

  • Using enthalpy changes of combustion, ΔHc

    • ΔrH = ∑ΔHc(reactants) - ∑ΔHc(products)

Calculating ΔHr  from ΔHf using Hess’s Law energy cycles

  • Knowing the enthalpy change of formation, ΔHf, allows us to determine the overall enthalpy change of a reaction, ΔHr

  • To do this, we follow these steps:

    1. Write the equation for the reaction

    2. Write the elements with the correct number of moles and state symbols underneath

    3. Draw upwards pointing arrows to each compound

    4. Write the appropriate values on the arrows and multiply by the number of moles

    5. In a cycle, go from the reactants to the products, changing the sign of the value if the arrow points in the opposite direction

Worked Example

Calculating the enthalpy change of reaction

Use the information in the table to calculate the enthalpy change for this reaction:

NH4NO3 (s)  +  ½C (s)  →  N2 (g)  +  2H2O (g)  +  ½CO2 (g)

Substance

C (s)

N2 (g)

H2O(g)

CO2 (g)

NH4NO3 (s)

Hfө / kJ mol–1

0

0

–242

–394

–365

Answer:

 Step 1: Write the balanced equation

wk eg step 1

Step 2: Write the elements with the correct number of moles and state symbols underneath

wk eg step 2

Step 3: Draw upwards pointing arrows to each compound

wk eg step3

Step 4: Write the appropriate values on the arrows and multiply by the number of moles

wk eg step 4

Step 5: In a cycle, go from the reactants to the products, changing the sign of the value if the arrow points in the opposite direction

wk eg step 5

ΔHrө = +365 - 484 - 197 = -316 kJ mol-1

  • The sign on -365 needs reversing as the cycle goes in the opposite direction to the arrow pointing upwards

  • There is no need to draw arrows from the elements to carbon and nitrogen as ΔHfө is 0 for elements

Examiner Tips and Tricks

Keep your enthalpy values inside their own brackets so that you don't accidentally lose a minus sign

Calculating ΔHf from ΔHc using Hess’s Law energy cycles

  • It can be difficult to find the enthalpy change of formation of compounds experimentally

  • However, many enthalpy changes of combustion can be measured experimentally so these can be used to find the enthalpy of formation

  • To do this, we follow these steps:

    1. Write the equation for the formation of the compound

    2. Write the combustion products below the equation

    3. Draw downward pointing arrows from each substance to its combustion products

    4. Write values on the arrows and multiply by the number of moles

    5. In a cycle, go from the reactants to the products, changing the sign of the value if the arrow points in the opposite direction

Worked Example

Calculating the enthalpy change of formation

Using the data provided, calculate the standard enthalpy change of formation, ΔHf, of propanone.

3C (s)  +     3H2 (g)   +      ½ O2 (g)               CH3COCH3 (l)

Substance

C (s)

H2 (g)

CH3COCH3 (l)

HCө / kJ mol–1

-394

-286

-1821

Answer:

  • Step 1: Write the balanced equation

wk eg step 1
  • Step 2:Write the combustion products below the equation

wk eg step 2
  • Step 3: Draw downward pointing arrows from each substance to its combustion product

wk eg step 3
  • Step 4: Write the appropriate values on the arrows and multiply by the number of moles

worked example step 4
  • Step 5: In a cycle, go from the reactants to the products, changing the sign of the value if the arrow points in the opposite direction

worked example step 5

ΔHfө = -1182 - 858 + 1821 = -219 kJ mol-1

  • The sign on -1821 needs reversing as the cycle goes in the opposite direction to the arrow pointing to the combustion products

Examiner Tips and Tricks

Don't forget to make sure the number of atoms for each element is balanced when drawing your cycle.

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