General Chemistry II

The enthalpy of ionisation (ΔHion) is the enthalpy change

involved in abstracting an electron from an atom or ion in the
gas phase

Mg(g) → Mg+(g) + e- (g) ΔH°ion = +738 kJ mole-1

Mg+(g) → Mg2+(g) + e- (g) ΔH°ion = +1451 kJ mole-1

(1st and 2nd -enthalpy of ionisation or ionisation energy- see

book of tables, Table 2)
 General Chemistry II

The electron affinity enthalpy or electron affinity (ΔH°el.aff. ) is

the enthalpy change on formation of a negative ion by taking
up an electron by a gaseous atom (or ion).

Cl(g) + e- → Cl- (g) ΔH°el.aff. = -349 kJ mol-1

(see book of tables, Table 2 for values of enthalpy of

ionisation and electron affinity enthalpy)
 General Chemistry II

The enthalpy of dissociation (ΔH°diss) , also called bond

enthalpy or bond energy, is the enthalpy change upon
breaking a chemical bond in a gaseous compound.

HCl(g) → H(g) + Cl(g) ΔH°diss = +432 kJ mol-1

average bond enthalpy, e.g. in water +464kJ/mol

 General Chemistry II

Enthalpy of atomisation (ΔHatom) : enthalpy change upon

transforming a substance (element or compound) into
gaseous atoms, always endotherm. e.g.

C(s) → C(g) ΔHatom = +716,7 kJ/mol (equal to ΔHsubl)

Na(s) → Na(g) ΔH = +107 kJ mol-1

 General Chemistry II

The reaction enthalpy (ΔHreaction) is the enthalpy change

associated with a reaction specified in a reaction equation.

For the reaction 2H2(g) + O2(g) → 2H2O

the standard reaction enthalpy is -571,6 kJ at 25°C : p = 1
atm., 2mole H2, 1mole O2, after reaction : 2 mole H2O, p =
1atm.
(not per mole ; per reaction)
standard enthalpy of combustion of dihydrogen (expressed
per mole H2) : -285.8 kJ mole-1
General Chemistry II

Crash of the Hindenburg

Zeppelin, 6 May 1937
 General Chemistry II
The enthalpy as state function

The enthalpy of a system is a state function and only

dependent on the state at the moment that the system is
being studied, and not dependent on the manner that this
state was reached.
The consequences of this are:
- Reversing a reaction or a process changes the sign of ΔH :

H = -H
 General Chemistry II
- Hess law : the enthalpy change of a global process is the
sum of the enthalpy changes of the different steps.
-if two reactions can be com-
bined mathematically to a
third reaction, the standard
reaction enthalpies may be
combined to the ΔH°reaction
of the third reaction (see also : Born-Haber cycle).
 General Chemistry II
Example : reaction of C with O2

2C(s) + 2O2 (g) → 2CO2(g) 2 x(ΔH°verbr) = 2x(-393,5) kJ

-[2CO(g) + O2(g) → 2CO2(g) ] -2 x(ΔH°verbr) = -2x(-283,0 kJ)
________________________________________________
2C(s) + O2(g) → 2CO(g) ΔH°reaction = -221,0 kJ

reaction 3 = 2x(reaction 1)- 2x(reaction 2) ΔH(3) = 2ΔH(1) -2ΔH(2)

Use standard enthalpies of combustion of C(s) and CO(g)

negative coefficients : bring product to other side of reaction arrow
General Chemistry II

(Hess diagram,
ΔH are the enthalpies of
combustion calcd per
mole C)
 General Chemistry II
The standard enthalpy of formation (ΔH°f) of a substance is the standard
enthalpy change of the reaction in which one mole of that substance is
formed from the composing parts in their reference state (expressed in
kJ/mole, see table 4 in book of tables).
reference state : most stable state of an element (ar 25°C)

The standard reaction-enthalpy can be calculated from the standard

enthalpies of formation of the reagents and the reaction products :
ΔH°reaction = ΣnΔH°f(reaction products) - ΣnΔH°f(reagents)
General Chemistry II
example : calculation of standard reaction enthalpy from ΔH°f

decomposiun of ammonium nitrate upon

heating :
NH4NO3(s) → N2O (g) + 2H2O (g)

ΔH°reaction = ΔH°f(N2O(g)) + 2 ΔH°f(H2O (g))

- ΔH°f(NH4NO3(s))

coefficients : do not forget !

Explosion in fertilizer
company →
General Chemistry II

Example : dissociation enthalpy of methane

ΔH°diss(CH4(g)) = ΔH°at(C(s)) + 2 ΔH°diss(H2(g)) - ΔH°f(CH4(g))

H°diss
CH4(g) C(g) + 4H(g)

H°at +2H°diss
H°f
C(s) + 2H2 (g)