Lecture 4: Hess’ Law

• Reading: Zumdahl 9.5

• Outline
– Definition of Hess’ Law
– Using Hess’ Law (many examples)
 Hess’ Law Defined
• From lecture 3: Enthalpy is a state function. As
such, ∆H for going from some initial state to some
final state is pathway independent.

• Hess’ Law: ∆H for a process involving the

transformation of reactants into products is not
dependent on pathway. Therefore, we can pick a
single-step pathway to calculate ∆H for a reaction.
Hess’ Law: An Example
 Using Hess’ Law
• When calculating ∆H for
N2 (g) + 2O2 (g) 2NO2 (g) a chemical reaction as a
single step, we can use
2NO2 (g)
combinations of
reactions as “pathways”
q to determine ∆H for our
N2 (g) + 2O2 (g) “single step” reaction.
 Example (cont.)
• Our reaction of interest is:
N2(g) + 2O2(g) 2NO2(g) ∆H = 68 kJ

• This reaction can also be carried out in two

steps:

N2 (g) + O2 (g) 2NO(g) ∆H = 180 kJ

2NO (g) + O2 (g) 2NO2(g) ∆H = -112 kJ
 Example (cont.)
• If we take the previous two reactions and add
them, we get the original reaction of interest:

N2 (g) + O2 (g) 2NO(g) ∆H = 180 kJ

2NO (g) + O2 (g) 2NO2(g) ∆H = -112 kJ

N2 (g) + 2O2 (g) 2NO2(g) ∆H = 68 kJ

 Example (cont.)
• Note the important things about this example, the
sum of ∆H for the two reaction steps is equal to
the ∆H for the reaction of interest.

• Big point: We can combine reactions of known

∆H to determine the ∆H for the “combined”
reaction.
 Hess’ Law: Details
• One can always reverse the direction of a
reaction when making a combined reaction.
When you do this, the sign of ∆H changes.

N2(g) + 2O2(g) 2NO2(g) ∆H = 68 kJ

2NO2(g) N2(g) + 2O2(g) ∆H = -68 kJ

 Details (cont.)
• The magnitude of ∆H is directly proportional to
the quantities involved (it is an “extensive”
quantity).
• As such, if the coefficients of a reaction are
multiplied by a constant, the value of ∆H is also
multiplied by the same integer.

N2(g) + 2O2(g) 2NO2(g) ∆H = 68 kJ

2N2(g) + 4O2(g) 4NO2(g) ∆H = 136 kJ

 Given the following reactions with associated ∆Hrxn:

+
∆H1

+ + ∆H2

+ + ∆H3

What is ∆Hrxn for the following:

+ + +

A. ∆H1 + ∆H2 + ∆H3 B. ∆H1 - ∆H2 + 2∆H3

C. ∆H1 + ∆H2 - ∆H3 D. -∆H1 - ∆H2 + ∆H3

 Using Hess’ Law
• When trying to combine reactions to form a
reaction of interest, one usually works
backwards from the reaction of interest.

• Example:
What is ∆H for the following reaction?
3C (gr) + 4H2 (g) C3H8 (g)
 Example (cont.)
3C (gr) + 4H2 (g) C3H8 (g) ∆H = ?

• You’re given the following reactions:

C (gr) + O2 (g) CO2 (g) ∆H = -394 kJ

C3H8 (g) + 5O2 (g) 3CO2 (g) + 4H2O (l) ∆H = -2220 kJ

H2 (g) + 1/2O2 (g) H2O (l) ∆H = -286 kJ

 Example (cont.)
• Step 1. Only reaction 1 has C (gr).
Therefore, we will multiply by 3 to get the
correct amount of C (gr) with respect to our
final equation.
Initial:
C (gr) + O2 (g) CO2 (g) ∆H = -394 kJ
Final:
3C (gr) + 3O2 (g) 3CO2 (g) ∆H = -1182 kJ
 Example (cont.)
• Step 2. To get C3H8 on the product side of
the reaction, we need to reverse reaction 2.
Initial:
C3H8 (g) + 5O2 (g) 3CO2 (g) + 4H2O (l) ∆H = -2220 kJ

Final:
3CO2 (g) + 4H2O (l) C3H8 (g) + 5O2 (g) ∆H = +2220 kJ
 Example (cont.)
• Step 3: Add two “new” reactions together
to see what is left:
3C (gr) + 3O2 (g) 3CO2 (g) ∆H = -1182 kJ
3CO2 (g) + 4H2O (l) C3H8 (g) + 5O2 (g) ∆H = +2220 kJ
2

3C (gr) + 4H2O (l) C3H8 (g) + 2O2 ∆H = +1038 kJ

 Example (cont.)
• Step 4: Compare previous reaction to final
reaction, and determine how to reach final
reaction:
3C (gr) + 4H2O (l) C3H8 (g) + 2O2 ∆H = +1038 kJ
H2 (g) + 1/2O2 (g) H2O (l) ∆H = -286 kJ

3C (gr) + 4H2 (g) C3H8 (g)

Need to multiply second reaction by 4

 Example (cont.)
• Step 4: Compare previous reaction to final
reaction, and determine how to reach final
reaction:
3C (gr) + 4H2O (l) C3H8 (g) + 2O2 ∆H = +1038 kJ
4H2 (g) + 2O2 (g) 4H2O (l) ∆H = -1144 kJ

3C (gr) + 4H2 (g) C3H8 (g)

 Example (cont.)
• Step 4 (cont.):

3C (gr) + 4H2O (l) C3H8 (g) + 2O2 ∆H = +1038 kJ

4H2 (g) + 2O2 (g) 4H2O (l) ∆H = -1144 kJ

3C (gr) + 4H2 (g) C3H8 (g) ∆H = -106 kJ

The combustion of methane has a ∆Hrxn of -802 kJ/mol:

CH 4 (g ) + 2O2 (g ) → CO2 (g ) + 2H 2O (g )

What is ∆Hrxn for the following?

1 1
CO2 (g ) + H 2O (g ) → CH 4 (g ) + O2 (g )
2 2

A. 802 kJ C. -1604 kJ

B. -401 kJ D. 401 kJ
 Another Example
• Calculate ∆H for the following reaction:
H2(g) + Cl2(g) 2HCl(g)
Given the following:
NH3 (g) + HCl (g) NH4Cl(s) ∆H = -176 kJ
N2 (g) + 3H2 (g) 2NH3 (g) ∆H = -92 kJ
N2 (g) + 4H2 (g) + Cl2 (g) 2NH4Cl(s) ∆H = -629 kJ
 Another Example (cont.)
• Step 1: Only the first reaction contains the
product of interest (HCl). Therefore,
reverse the reaction and multiply by 2 to get
stoichiometry correct.
NH3 (g) + HCl (g) NH4Cl(s) ∆H = -176 kJ

2NH4Cl(s) 2NH3 (g) + 2HCl (g) ∆H = 352 kJ

 Another Example (cont.)
• Step 2. Need Cl2 as a reactant, therefore,
add reaction 3 to result from step 1 and see
what is left.
2NH4Cl(s) 2NH3 (g) + 2HCl (g) ∆H = 352 kJ
N2 (g) + 4H2 (g) + Cl2 (g) 2NH4Cl(s) ∆H = -629 kJ

N2 (g) + 4H2 (g) + Cl2 (g) 2NH3(g) + 2HCl(g)

∆H = -277 kJ
 Another Example (cont.)
• Step 3. Use remaining known reaction in
combination with the result from Step 2 to
get final reaction.

N2 (g) + 4H2 (g) + Cl2 (g) 2NH3(g) + 2HCl(g) ∆H = -277 kJ

( N2 (g) + 3H2(g) 2NH3(g) ∆H = -92 kJ)

H2(g) + Cl2(g) 2HCl(g) ∆H = ?

Need to take middle reaction and reverse it

 Another Example (cont.)
• Step 3. Use remaining known reaction in
combination with the result from Step 2 to
get final reaction.

N2 (g) + 4H2 (g) + Cl2 (g) 2NH3(g) + 2HCl(g) ∆H = -277 kJ

1
2NH3(g) 3H2 (g) + N2 (g) ∆H = +92 kJ

H2(g) + Cl2(g) 2HCl(g) ∆H = -185 kJ