ENERGY

Chem 02 Lecture of Mr. JV Nazareno

 O UT LIN E:

¡Thermochemical Equations

¡Enthalpies of Reaction
¡Heats of Formation
¡Hess’s Law
 T HERM O C HEM IC AL EQ UAT IO N S

§ These are balanced chemical equations

that show the associated enthalpy
change.

Ex:

2 𝐻$ (&) + 𝑂$ (&) → 2 𝐻$ 𝑂 (&) ∆𝐻 = −483.6 𝑘𝐽

 T HERM O C HEM IC AL EQ UAT IO N S

§ USEFUL GUIDELINES IN INTERPRETING

THERMOCHEMICAL EQUATIONS:

1. Enthalpy is an extensive property

The magnitude of ΔH is directly

proportional to the amount of reactant
consumed in the process.
 T HERM O C HEM IC AL EQ UAT IO N S

ACTIVITY:

For the reaction:

𝐶𝐻6 (&) + 2 𝑂$ (&) → 2 𝐻$ 𝑂 (7) + 𝐶𝑂$ (&)
∆𝐻 = −890 𝑘𝐽

Calculate the amount of heat released when 4.50

grams of methane is burned in a constant pressure
system.
 T HERM O C HEM IC AL EQ UAT IO N S

§ USEFUL GUIDELINES IN INTERPRETING

THERMOCHEMICAL EQUATIONS:

2. Enthalpy change for a reaction is equal in

magnitude, but opposite in sign, to ΔH of the
reverse reaction.
 T HERM O C HEM IC AL EQ UAT IO N S

Using the previous reaction:

𝐶𝐻6 (&) + 2 𝑂$ (&) → 2 𝐻$ 𝑂 (7) + 𝐶𝑂$ (&)

∆𝐻 = −890 𝑘𝐽

Then:
2 𝐻$ 𝑂 (7) + 𝐶𝑂$ (&) → 𝐶𝐻6 (&) + 2 𝑂$ (&)
∆𝐻 = 890 𝑘𝐽
 T HERM O C HEM IC AL EQ UAT IO N S

§ USEFUL GUIDELINES IN INTERPRETING

THERMOCHEMICAL EQUATIONS:

3. Enthalpy change for a reaction depends on

the state of reactants and products.
 T HERM O C HEM IC AL EQ UAT IO N S

LET’S RATIONALIZE!

𝐶𝐻6 (&) + 2 𝑂$ (&) → 2 𝐻$ 𝑂 (7) + 𝐶𝑂$ (&)

∆𝐻 = −890 𝑘𝐽

Then:
𝐶𝐻6 (&) + 2 𝑂$ (&) → 2 𝐻$ 𝑂 (&) + 𝐶𝑂$ (&)
∆𝐻 = −802 𝑘𝐽
 EN T HALP Y O F REAC T IO N S

§ HOW IS ENTHALPY
MEASURED???

1. Calorimetry: experimental
measurement of heat flow of
a process at constant
pressure.

Figure 1. A basic calorimeter

 EN T HALP Y O F REAC T IO N S

§ HOW IS ENTHALPY
MEASURED???

2. Hess’s Law: based on the

tabulated ΔH values of
other reactions.

Figure 2. Germain Henri Hess

 EN T HALP Y O F REAC T IO N S

Hess’s Law of Constant Heat Summation states

that:

“if a reaction is carried out in a series of

steps, ΔH rxn will be equal to the sum of the
enthalpy changes for the individual steps.
 T HERM O C HEM IC AL EQ UAT IO N S

WORKED EXAMPLE:

Calculate the the enthalpy of combustion of C

(carbon) to CO (carbon monoxide):

𝐶 (:) + 1<2 𝑂$ (=) → 𝐶𝑂 (=) ∆H = −? ? ? kJ

𝐶𝑂 (𝑔) + 1<2 𝑂2 (𝑔) → 𝐶𝑂2 (𝑔) ∆𝐻 = −283.0 𝑘𝐽

𝐶 (C) + 𝑂$ (&) → 𝐶𝑂$ (&) ∆𝐻 = −393.5 𝑘𝐽

 EN T HALP Y O F REAC T IO N S

Hess’s Law of Constant Heat Summation states

that:

“if a reaction is carried out in a series of

steps, ΔH rxn will be equal to the sum of the
enthalpy changes for the individual steps.

Figure 3. Enthalpy Diagram for the Combustion of Carbon

 EN T HALP Y O F REAC T IO N S

WORKED EXAMPLE:

Calculate the enthalpy for the reaction, given the

following information:

𝑁𝑂 (&) + 𝑂 (&) → 𝑁𝑂$ (&) ∆𝐻 = ? ? ? . ? 𝑘𝐽

𝑁𝑂 (&) + 𝑂F (&) → 𝑁𝑂$ (&) + 𝑂$ (&) ∆𝐻 = −198.9 𝑘𝐽

𝑂F (&) → 3<2 𝑂$ (&) ∆𝐻 = −142.3 𝑘𝐽

𝑂$ (&) → 2 𝑂 (&) ∆𝐻 = 495.0 𝑘𝐽

 EN T HALP Y O F REAC T IO N S

ACTIVITY:

Calculate the enthalpy for the reaction, given the

following information:

𝐶$ 𝐻6 (&) + 6 𝐹$ (&) → 2 𝐶𝐹6 (&) + 4 𝐻𝐹 (&) ∆𝐻 = ? ? ? . ? 𝑘𝐽

𝐻$ (&) + 𝐹$ (&) → 2 𝐻𝐹 (&) ∆𝐻 = −537 𝑘𝐽

𝐶 (I) + 2 𝐹$ (&) → 𝐶𝐹6 (&) ∆𝐻 = −680 𝑘𝐽

2 𝐶 (I) + 2 𝐻$ (&) → 𝐶$ 𝐻6 (&) ∆𝐻 = 52.3 𝑘𝐽

 EN T HALP Y O F REAC T IO N S

§ HOW IS ENTHALPY MEASURED???

3. Enthalpy (or heats) of Formation, ΔH˚ f :

Ø makes use of the thermochemical data of the
formation of a compound from its constituent
elements.
Ø is defined by a set of conditions known as
standard states (1 atm and usually 298K)
 EN T HALP Y O F REAC T IO N S

Consider the formation of liquid ethanol at

standard state:

2 𝐶 (𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒) (I) + 3 𝐻$ (&) + 1<2 𝑂$ (&) → 𝐶$ 𝐻Q 𝑂 (7)

∆𝐻˚S = −277.7 𝑘𝐽

§ Aren’t there other elemental forms of carbon

and oxygen??? What are they?
 EN T HALP Y O F REAC T IO N S

§ POINTS TO PONDER…

ü ΔH˚ f (expressed in kJ/mol) is always in terms of

1 mol of compound formed from its elements,
with all substances at their standard states (most
stable).

ü Therefore, all elements in their most stable

form will have a standard enthalpy of formation
of ZEROOOOOOOO!!!
 EN T HALP Y O F REAC T IO N S

ACTIVITY:

For which of the following reactions at 25˚C would the

enthalpy change represent a standard enthalpy of
formation? For those that do not, what changes to the
reaction conditions are necessary?

2 Na (V) + 1<2 O$ (&) → 𝑁𝑎$ O (V)

2 𝐾(I) + 𝐶𝑙$ (&) → 2 𝐾𝐶𝑙 (I)

𝐶Q 𝐻Z$ 𝑂Q (I) → 6 𝐶 (𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒)I + 6 𝐻$ (&) + 3 𝑂$ (&)

 EN T HALP Y O F REAC T IO N S

Let’s now consider the combustion of propane:

𝐶F 𝐻[ (&) + 5 𝑂$ (&) → 3 𝐶𝑂$ (&) + 4 𝐻$ 𝑂 (7)

§ Write the formation reactions of all compounds

found within the equation and try to compute
for ΔH˚ rxn (ΔH˚ f of C 3H 8 = −103.85 kJ/mol, CO 2
and H 2O is found in text).
 EN T HALP Y O F REAC T IO N S

Figure 4. Enthalpy Diagram for the Combustion of Propane

 EN T HALP Y O F REAC T IO N S

The general result for any equation is that the

standard heat of reaction is equal to the sum of
the standard heats of formation of the products
minus the standard heats of formation of the
reactants:

∆𝐻˚ \]^ = Σ 𝑛∆𝐻˚S 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − Σ 𝑚∆𝐻˚S 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

 EN T HALP Y O F REAC T IO N S

WORKED EXAMPLE:

Calculate the standard enthalpy change for the

following reaction:

SiCl4 (l) + 2 H2O (l) → SiO2 (s) + 4 HCl (g)

−640.1 −285.8 −910.9 −92.3

kJ/mol kJ/mol kJ/mol kJ/mol