Hess’s Law and Enthalpy of Formation

Part A – Enthalpy of a Chemical Reaction (∆Hrxn)

The enthalpy of a reaction (∆H, also written as ∆Hrxn) is the amount of heat that is either absorbed or
released during a chemical process. If the reaction absorbs heat, it is endothermic and has a positive
enthalpy of reaction (+∆H). If the reaction releases heat, it is exothermic and has a negative enthalpy of
reaction (-∆H). It is an extensive property, meaning that if the chemical equation of a certain reaction is
manipulated, the ∆H of that reaction must also be manipulated in the same way. For example, if a
chemical equation is multiplied by a factor of two, the enthalpy of the reaction must also be multiplied by
two. If an equation is flipped, then the sign of the enthalpy must also be flipped.

Practice
For each of the following equations, what is the ∆H of the reaction if each of the following manipulations
are performed?

a) What is the new value of ∆H if the following equation is multiplied by ½?

2 H2(g) + O2(g) → 2 H2O(l) ∆H = -572 kJ

𝟏𝟏�
𝟐𝟐 [2 H2(g) + O2(g) → 2 H2O(l)] 𝟏𝟏� [∆H
𝟐𝟐 = -572 kJ]

Multiply by 1/2 Multiply by 1/2

H2(g) + 𝟏𝟏�
𝟐𝟐 O2(g) → 2 H2O(l) ∆H = -286 kJ

b) What is the new value of ∆H if the following equation is both multiplied by 3 and flipped?

2 CO2(g) + 3 H2O(l) → C2H5OH(l) + 3 O2(g) ∆H = 1366.8 kJ

3[2 CO2(g) + 3 H2O(l) → C2H5OH(l) + 3 O2(g)] -3[∆H = 1366.8 kJ]

Multiply by 3 Flip reactants and products Change sign and multiply by 3

9O2(g) + 3 C2H5OH(l) → 6 CO2(g) + 9H2O(l) ∆H = -4100.4 kJ

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 Example #1
a) What is the new value of ∆H if the following equation is multiplied by 2?

CO(g) + ½ O2(g) → CO2(g) ∆H = -238.0 kJ

b) What is the new value of ∆H if the following equation is multiplied by 1�2 and flipped?

2 MgO(s) → O2(g) + 2 Mg(s) ∆H = 1203.2 kJ

Part B – Hess’s Law

Hess’s Law states that if a reaction can be written as the sum of several stepwise reactions, then enthalpy
change of the total (‘goal’) reaction equals the sum of the enthalpy changes of the various steps. In order
to be able to sum the enthalpies of each of the stepwise reactions to equal the overall ‘goal’ reaction, the
steps need to have the correct stoichiometric ratios for each species and also have the species on the
correct reactants and products side in the correct phase. Intermediate species, compounds that appear as
both a product and a reactant and do not appear in the overall equation, can be canceled.

Practice
Calculate ∆H for the process:

‘Goal’ Equation C(s) + O2(g) → CO2(g) ∆H = ??

from the following information:

Equation 1 C(s) + O2(g) → CO(g) + 1�2 O2(g) ∆H = -111 kJ
Equation 2 CO(g) + 1�2 O2(g) → CO2(g) ∆H = -283 kJ

When the two equations are added together, their enthalpies of reaction are also added together. CO and
only the 1�2 O2 are intermediate species and can be canceled.

Equation 1 C(s) + O2(g) → CO(g) + 1�2 O2(g) ∆H = -111 kJ

Equation 2 CO(g) + 1�2 O2(g) → CO2(g) ∆H = -283 kJ
+
‘Goal’ Equation C(s) + O2(g) → CO2(g) ∆H = -394 kJ

This figure is a visual representation of

Equations 1 and 2 being added together to
equal the ‘goal’ equation.

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 Example #2
Calculate ∆H° for the process:

‘Goal’ Equation Sb(s) + 5�

2 Cl2(g) → SbCl5(g) ∆H = ??

from the following information:

Equation 1 Sb(s) + 3�2 Cl2(g) → SbCl3(g) ∆H = -314 kJ

Equation 2 SbCl3(s) + Cl2(g) → SbCl5(g) ∆H = -80 kJ

Many times the chemical equations for each of the steps and their respective ∆H’s must be manipulated
(as in Part A) to have the correct stoichiometric coefficients for each species and have them on the correct
reactants or products side.

Practice
Calculate ∆H for the process:

‘Goal’ Equation C(s) + H2O(g) → CO(g) + H2(g) ∆H = ??

from the following information:

Equation 1 CO2(g) → C(s) + O2(g) ∆H = 393.5 kJ

Equation 2 2 CO(g) + O2(g) → 2 CO2(g) ∆H = -566.0 kJ
Equation 3 2 H2O(g) → 2 H2(g) + O2(g) ∆H = 483.6 kJ

In this example, Equations 1, 2, and 3 don’t directly add together to equal the ‘goal’ equation. Therefore,
these equations will need to be manipulated before they can be added together. The following goes
through the manipulation of each equation:

Equation 1: You’ll notice that the C(s) is on the products side when it should be on the reactants side,
according to the ‘goal’ equation. That is how you know this equation needs to be flipped so that the C(s)
is on the reactants side. CO2(g) and O2(g) do not appear in the ‘goal’ equation, so they are intermediate
species that will cancel.

C(s) + O2(g) → CO2(g) ∆H = -393.5 kJ

Flip reactants and products Change sign

Equation 2: You’ll notice that the CO(g) is on the reactants side, but it should be on the products side in
the ‘goal’ equation. You’ll also notice that the coefficient is incorrect. In this equation, its coefficient is 2,

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 while in the ‘goal’ equation, its coefficient is 1. Therefore, this equation needs to be both flipped and
multiplied by 1�2. CO(g) and O2(g) are once again intermediate species in this equation.
Multiply by 𝟏𝟏�𝟐𝟐

CO2(g) → CO(g) + 𝟏𝟏� O2(g)

𝟐𝟐 ∆H = 𝟏𝟏�𝟐𝟐 [+566.0 kJ]

Flip reactants and products Change sign

and multiply by 𝟏𝟏�𝟐𝟐

Equation 3: In this equation, the H2O(g) and H2(g) are on their correct respective side, but both have
incorrect coefficients. In this equation, both have coefficients of 2, while in the ‘goal equation, both have
coefficients of 1. Therefore, this equation only needs to be multiplied by 1�2.

Multiply by 𝟏𝟏�𝟐𝟐 Multiply by 𝟏𝟏�𝟐𝟐

H2O(g) → H2(g) + 𝟏𝟏� O2(g)

𝟐𝟐 ∆H = 𝟏𝟏�𝟐𝟐 [483.6.0 kJ]

Add the manipulated Equations 1, 2, and 3 together and cancel intermediate species:

C(s) + O2(g) → CO2(g) ∆H = -393.5 kJ

CO2(s) → CO(g) + 𝟏𝟏�𝟐𝟐 O2(g) ∆H = 283.0 kJ
+ H2O(g) → H2(g) + 𝟏𝟏�𝟐𝟐 O2(g) ∆H = 241.8 kJ

C(s) + H2O(g) → CO(g) + H2(g) ∆H = 131.3 kJ

Example #3
Calculate ∆H° for the process:

‘Goal’ Equation CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l) ∆H = ??

from the following information:

Equation 1 CH2O(g) + H2O(g) → CH4(g) + O2(g) ∆H = 275.6 kJ

Equation 2 CH2O(g) + O2(g) → CO2(g) + H2O(g) ∆H = -526.7 kJ
Equation 3 H2O(l) → H2O(g) ∆H = 44.0 kJ

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 Part C – Hess’s Law and Standard Enthalpy of Formation (∆H°f)

The formation of a compound from its elements in their standard state is a special enthalpy called the
standard enthalpy of formation (∆H°f). Standard state (denoted by the ‘°’ following the ΔH) is defined
as a substance in its natural form at 1 atm pressure (for gases), 1 M concentration (for solutions), and at
298 K. For example, NaCl(s) is formed from its elements Na(s) and Cl2(g) in the following chemical
reaction:

Na(s) + 1� Cl2(g)
2 → NaCl(s) ∆H°f = -411.2 kJ/mol

The formation of 1 mole of NaCl(s) releases 411.2 kJ of heat. These equations are typically written with 1
mol of product being formed, so fractions are typically used (if needed) for the reactants to balance the
chemical equation. The ∆H°f is defined as zero for elements in their standard form.

If this concept is combined with Hess’s Law, standard enthalpies of formation of compounds in a
chemical reaction can be used to determine the enthalpy of the entire reaction.

Practice
Determine the ∆H°rxn of the reaction below using the enthalpies of formation of each of the species.

‘Goal’ Equation 3 NO2(g) + H2O(l) → 2 HNO3(aq) + NO(g) ∆H°rxn = ??

The enthalpy of formation equation for each of the species is the following:

Equation 1 1�
2 N2(g) + O2(g) → NO2(g) ∆H°f = 33.2 kJ/mol
Equation 2 H2(g) + 1�2 O2(g) → H2O(l) ∆H°f = -285.83 kJ/mol
Equation 3 1� H2(g) + 1� N2(g) + 3� O2(g) → HNO3(aq) ∆H°f = -207.4 kJ/mol
2 2 2
Equation 4 1� N2(g) + 1� O2(g) → NO(g) ∆H°f = 90.25 kJ/mol
2 2

In order to be able to add these equations and cancel intermediate species using Hess’s Law, Equations 1-
4 need to be manipulated as in Part A:

Equation 1 3 NO2(g) → 3�2N2(g) + 3 O2(g) -3(∆H°f = 33.2 kJ/mol)

Equation 2 H2O(l) → H2(g) + 1�2 O2(g) -(∆H°f = -285.83 kJ/mol)
Equation 3 H2(g) + N2(g) + 3 O2(g) → 2 HNO3(aq) 2(∆H°f = -207.4 kJ/mol)
1� N2(g) + 1� O2(g) → NO(g) ∆H°f = 90.25 kJ/mol
Equation 4 2 2
+
3 NO2(g) + H2O(l) → 2 HNO3(aq) + NO(g) ∆H°rxn = -138.3 kJ/mol

Notice for each substance, the ΔH°f is multiplied by its stoichiometric coefficient. In addition, the
formation equation for each of the reactants had to be flipped to get the substance on the reactant side.
Thus, when using heats of formation, the Hess’s Law process can be simplified to the following equation:

∆𝑯𝑯𝒐𝒐𝒓𝒓𝒓𝒓𝒓𝒓 = � 𝒏𝒏 × ∆𝑯𝑯𝒐𝒐𝒇𝒇 (𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑) − � 𝒏𝒏 × ∆𝑯𝑯𝒐𝒐𝒇𝒇 (𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓)

In this equation, the enthalpy of the total reaction is equal to the sum of the enthalpy of formation of the
products multiplied by their respective stoichiometric coefficient (n) minus the sum of the enthalpy of

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formation of the reactants multiplied by their respective stoichiometric coefficient (n). This equation
above can also be used to calculate the enthalpy of the chemical reaction:

3 NO2(g) + H2O(l) → 2 HNO3(aq) + NO(g) ∆H°rxn = ??

∆𝑯𝑯𝒐𝒐𝒓𝒓𝒓𝒓𝒓𝒓 = �𝟐𝟐�∆𝑯𝑯𝒐𝒐𝒇𝒇 𝒐𝒐𝒐𝒐 𝑯𝑯𝑯𝑯𝑶𝑶𝟑𝟑 � + �∆𝑯𝑯𝒐𝒐𝒇𝒇 𝒐𝒐𝒐𝒐 𝑵𝑵𝑵𝑵�� − �𝟑𝟑�∆𝑯𝑯𝒐𝒐𝒇𝒇 𝒐𝒐𝒐𝒐 𝑵𝑵𝑶𝑶𝟑𝟑 � + �∆𝑯𝑯𝒐𝒐𝒇𝒇 𝒐𝒐𝒐𝒐 𝑯𝑯𝟐𝟐 𝑶𝑶��

𝒌𝒌𝒌𝒌 𝒌𝒌𝒌𝒌 𝒌𝒌𝒌𝒌 𝒌𝒌𝒌𝒌 𝒌𝒌𝒌𝒌

= �𝟐𝟐 �−𝟐𝟐𝟐𝟐𝟐𝟐. 𝟒𝟒 � + �𝟗𝟗𝟗𝟗. 𝟐𝟐𝟐𝟐 �� − �𝟑𝟑 �𝟑𝟑𝟑𝟑. 𝟐𝟐 � + �−𝟐𝟐𝟐𝟐𝟐𝟐. 𝟖𝟖𝟖𝟖 �� = −𝟏𝟏𝟏𝟏𝟏𝟏. 𝟑𝟑
𝒎𝒎𝒎𝒎𝒎𝒎 𝒎𝒎𝒎𝒎𝒎𝒎 𝒎𝒎𝒎𝒎𝒎𝒎 𝒎𝒎𝒎𝒎𝒎𝒎 𝒎𝒎𝒎𝒎𝒎𝒎

Practice
Calculate the ∆H°rxn of the reaction below using the enthalpies of formation provided:

C2H5OH(l) + 3 O2(g) → 3 H2O(l) + 2 CO2(g) ∆H°rxn = ??

Substance ∆H°f
C2H5OH(l) -278 kJ/mol
H2O(l) -286 kJ/mol
CO2(g) -394 kJ/mol

Since O2(g) is already in its standard state, its ∆H°f is 0.

𝒌𝒌𝒌𝒌 𝒌𝒌𝒌𝒌 𝒌𝒌𝒌𝒌 𝒌𝒌𝒌𝒌 𝒌𝒌𝒌𝒌

∆𝑯𝑯𝒐𝒐𝒓𝒓𝒓𝒓𝒓𝒓 = �𝟑𝟑 �−𝟐𝟐𝟐𝟐𝟐𝟐 � + 𝟐𝟐 �−𝟑𝟑𝟑𝟑𝟑𝟑 �� − ��−𝟐𝟐𝟐𝟐𝟐𝟐 � + 𝟑𝟑 �𝟎𝟎 �� = −𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏
𝒎𝒎𝒎𝒎𝒎𝒎 𝒎𝒎𝒎𝒎𝒎𝒎 𝒎𝒎𝒎𝒎𝒎𝒎 𝒎𝒎𝒎𝒎𝒎𝒎 𝒎𝒎𝒎𝒎𝒎𝒎

Example #4
Calculate the ∆H°rxn of the reaction below using the enthalpies of formation provided:

SiCl4(l) + 2 H2(g) → Si(s) + 4 HCl(g) ∆H°rxn = ??

Substance ∆H°f
SiCl4(l) -687 kJ/mol
HCl(g) -92 kJ/mol

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Part D – Extra Practice
1. Calculate ∆H for the process: Hg2Cl2(s) → 2 Hg(l) + Cl2(g)
Hg(l) + Cl2(g) → HgCl2(s) ∆H = -224 kJ
Hg(l) + HgCl2(s) → Hg2Cl2(s) ∆H = -41.2 kJ

2. Calculate the ∆H for the process: Zn(s) + S(s) + 2 O2(g) → ZnSO4(s)

ZnS(s) → Zn(s) + S(s) ∆H = 206.0 kJ
½ ZnS(s) + O2(g) → ½ ZnSO4(s) ∆H = -388.4 kJ

3. Calculate the ∆H for the process: C(s, graphite) + 2 H2(g) → CH4(g)

C(s, graphite) + O2(g) → CO2(g) ∆H = -393.51 kJ
H2(g) + ½ O2(g) → H2O(l) ∆H = -285.83 kJ
CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l) ∆H = -892 kJ

4. Calculate ∆H for the process: 6 C(s, graphite) + 3 H2(g) → C6H6(l)

2 C6H6(l) + 15 O2(g) → 12 CO2(g) + 6 H2O(l) ∆H = -6542 kJ
C(s, graphite) + O2(g) → CO2(g) ∆H = -393.51 kJ
H2(g) + ½ O2(g) → H2O(l) ∆H = -285.83 kJ

5. Calculate the ∆H°rxn of each of the reactions below using the enthalpies of formation provided:

a) 4 NH3(g) + 7 O2(g) → 4 NO2(g) + 6 H2O(g)

Substance ∆H°f
NH3(g) -45.9 kJ/mol
NO2(g) 33.2 kJ/mol
H2O(g) -241.82 kJ/mol

b) 2 Al(s) + Fe2O3(s) → Al2O3(s) + 2 Fe(s)

Substance ∆H°f
Fe2O3(s) -824.2 kJ/mol
Al2O3(s) -1676 kJ/mol

c) CH4(g) + N2(g) → HCN(g) + NH3(g)

Substance ∆H°f
CH4(g) -74.6 kJ/mol
HCN(g) 135.5 kJ/mol
NH3(g) -45.9 kJ/mol

d) Si(s) + 2 F2(g) → SiF4(g)

Substance ∆H°f
SiF4(g) -1615.0 kJ/mol

6. The ∆H°rxn for the decomposition of silver nitrate is +157.3 kJ/mol. If the standard enthalpy of
formation of AgNO3(s) is -123.02 kJ/mol, calculate the standard enthalpy of formation of
AgNO2(s).
2 AgNO3(s) → 2 AgNO2(s) + O2(g) ΔH = 157.3 kJ

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