Chemistry 5

Chapter-7
Thermochemistry
Part-3

23 October 2002
 Enthalpies of Reaction
ƒ A thermochemical equation combines
• balanced chemical equation
• reaction enthalpy, ∆H
∆H of reaction– heat change at constant P– ignores work
done by/on the system in moving from initial to final state.

ƒ Reaction enthalpy
The reaction enthalpy is the change in enthalpy for
stoichiometric number of moles of reactants in the
chemical equation:
CH4(g) + 2O2(g) Æ CO2(g) + 2H2O(l) ∆H = -890 kJ
ƒ Things to pay attention to:
• ∆H is extensive
Enthalpy change is directly proportional to
amounts of substances in system.
• ∆H depends on direction
∆H changes sign when a process is reversed; that
is, ∆Η is a state function, and reverse intial/final
states.
• State of reactants/products
Enthalpy change depends on the state– gas, liquid or
solid– of substances in chemical equation.
∆H is state function and changing state of
reactant/product changes intial/final state.
 Enthalpies of Reaction-- Example
ƒ Thermochemical Equation:
CH4(g) + 2O2(g) Æ CO2(g) + 2H2O(l) ∆H = -890 kJ

ƒ Change Number of Moles

2CH4(g) + 4O2(g) Æ 2CO2(g) + 4H2O(l) ∆H = -1780 kJ
(∆H is extensive property)

ƒ Change Direction of Reaction

CO2(g) + 2H2O(l) Æ CH4(g) + 2O2(g) ∆H = +890 kJ
(∆H is state function)

ƒ Change State of Reactants and Products

CH4(g) + 2O2(g) Æ CO2(g) + 2H2O(g) ∆H = -802 kJ
It takes heat (∆Hvap) to change water from liquid to gas
state, and thus heat of reaction is reduced.

How do we generalize this idea?

Combining Thermochemical Eqns
ƒ Thermochemical Equations:
CH4(g) + 2O2(g) Æ CO2(g) + 2H2O(l) ∆H = -890 kJ
2H2O(l) Æ 2H2O(g) ∆H = +88 kJ
CH4(g) + 2O2(g) Æ CO2(g) + 2H2O(g) ∆H = -802 kJ

ƒ Hess’s Law
The overall reaction enthalpy is the sum of reaction
enthalpies of the steps into which the reaction is divided.
If a process occurs in steps– even if these are
hypothetical– then the enthalpy change for the overall
process is the sum of the enthalpy changes of the
individual steps!

CH4(g) + 2O2(g) initial state

ENTHALPY

CO2(g) + 2H2O(l) final state

 Hess’s Law– Example-2
S(s) + 3/2O2(g) Æ SO3(g) ∆H = ?

S solid
+O2

+ 3/2 O2
SO2 gas

SO3 gas + 1/2O2

ƒ Hess’s Law
1. S(s) + O2(g) Æ SO2(g) ∆H1 = -320.5 kJ
2. SO2(g) + 1/2O2(g) Æ SO3(g) ∆H2 = -75.2 kJ
S(s) + 3/2O2(g) Æ SO3(g)

∆Hrxn = ∆H1 + ∆H2

= -320.5 + -75.2
= -395.7 kJ
 Standard Enthalpies
ƒ Standard Enthalpy of Formation, ∆Hfo
of a substance is the enthalpy change that occurs in the
formation of one mole of the substance in the standard
state from reference form of the elements in their
standard states.
ƒ Pure Elements in Reference Form?
Generally, most stable form of elements in standard
state; for example: H is H2(g), O is O2(g), Na is Na(s)
• pure elements, reference form:
The standard enthalpy of formation of a pure
element in its reference form is zero, O.
 ∆Hfo: Examples
ƒ

ƒ Formation Reactions:
C(s, graphite) + O2(g) Æ CO2(g)
C(s, graphite) + 2H2(g) Æ CH4(g)
1/2N2(g) + 3/2H2(g) Æ NH3(g)
1/2N2(g) + 1/2O2(g) Æ NO(g)
1/2N2(g) + O2(g) Æ NO (g)
2

Na(s) + 1/2Cl2(g) Æ NaCl(s)

 Standard Enthalpies of RXN
ƒ ∆Hfo & ∆Horxn
• Standard enthalpies of formation tabulated since they
can be used to calculate enthalpy of reaction.
• How? Use state function property of H– does not
matter what pathway we take– and design path
through elements in their standard forms.

∆H = Σvp∆Hfo(products) – Σvr∆Hfo(reactants)

ƒ Example: NO(g) + (1/2) O2(g) Æ NO2(g)

• ∆Horxn = ∆Hf(NO2) – ∆Hf(NO) – 1/2∆Hf(O2)
• determine enthalpies of formation

NO(g) + (1/2) O2(g)

ENTHALPY

NO2(g)

(1/2) N2(g) + O2(g)

 RXN of Al & Iron Oxide

ƒ Overall Chemical Reaction

2 Al + Fe2O3 Æ Al2O3 + 2Fe

Is reaction exothermic or endothermic?

ƒ Enthalpy of Reaction:
∆H = Σvp∆Hfo(products) – Σvr∆Hfo(reactants)

= ∆Hf(Al2O3) + 2∆Hf(Fe) – 2∆Hf(Al) – ∆Hf(Fe2O3)

= -1676 + 2(0) – 2(0) - -824
= -852 kJ/mol

ƒ Demonstration– Observations?
• After starting, the reaction proceeds vigorous
• A lot of heat is released!!

∆Hfo (kJ/mol)
Al(s) 0
Al2O3(s) -1676
Fe(s) 0
Fe2O3(s) -824
 Ionic Reactions in Water?

ƒ Standard State
• conditions:
Many chemical reactions proceed in aqueous
solution (e.g., biochemical reactions) and involve
ionic species, such as protons and metal cations.
Standard State: 1M concentration
• reference state:
To determine enthalpies of formation for ions there
is new issue– cannot create ion of single type in
chemical reaction.
Therefore, define a reference state to which
compare enthalpies of formation of other ions:
∆Hfo (H+) = 0
ƒ
 Enthalpies of Ionic Reactions
ƒ When 50.0ml of 0.100M Na2SO4(aq) is mixed with
25.0ml of 0.200M AgNO3(aq), a white ppt forms.
• Net ionic reaction?
2Ag+(aq) + SO42-(aq) Æ Ag2SO4(s)
• Given ∆Hfo(Ag2SO4(s)) = -715 kJ/mol, calculate
∆Hrxn; is reaction endo or exothermic?

∆Hrxn = ∆Hf(Ag2SO4) – 2∆Hf(Ag+) – ∆Hf(SO42-)

= -715 – 2(106) – (-909)
= -18 kJ/mol

Slightly Exothermic
total enthalpy for experiment = 2.5x10-3mol x -18kJ/mol
= -4.5x10-2 kJ

• If the solution starts at 25.0oC, will the final

temperature be high or lower, and by how
much?
Slightly Higher
Assume: (i) specific heat = that of water, 4.18 J/g-K
(ii) density = that of water 1g/ml
(iii) solve using q = m x specific heat x ∆T
Food & Enthalpies of Reactions
ƒ

ƒ Overall Thermochemical Reactions:

• Carbohydrate– sucrose:
C12H22O11 + 12O2 Æ 12CO2(g) + 11H2O(l)

• Fat
C12H24 + 36O2 Æ 12CO2(g) + 12H2O(l)

ƒ +/- of different types of fuels?

∆H(carbohydrate) ~ 17 kJ/g
∆H(fat) ~ 38 kJ/g
There is approximate 2x more energy store per gram in
fat than carbohydrates…….hence, if you are a bear
sleeping for the winter it is much better to store
needed fuel as fat!