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Chapter-7
Thermochemistry
Part-3
23 October 2002
Enthalpies of Reaction
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.
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
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
Thermochemical Equation:
CH4(g) + 2O2(g) Æ CO2(g) + 2H2O(l) ∆H = -890 kJ
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!
S solid
+O2
+ 3/2 O2
SO2 gas
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)
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
∆H = Σvp∆Hfo(products) – Σvr∆Hfo(reactants)
NO2(g)
Enthalpy of Reaction:
∆H = Σvp∆Hfo(products) – Σvr∆Hfo(reactants)
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?
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
Enthalpies of Ionic Reactions
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?
Slightly Exothermic
total enthalpy for experiment = 2.5x10-3mol x -18kJ/mol
= -4.5x10-2 kJ
• Fat
C12H24 + 36O2 Æ 12CO2(g) + 12H2O(l)