Topic 2.

1
ENERGETICS
Measuring and Calculating Enthalpy Changes
Mean Bond Dissociation Enthalpies
ess! "a#
ENTHALPY CHANGES
1. Exothermic and endothermic reactions
When a chemical reaction takes place, the products and reactants have different stabilities
and thus there is a change in potential energy. However since total energy is always
conserved, any change in potential energy must be balanced by an equal and opposite
change in kinetic energy.
The lower the chemical potential energy of a given chemical species, the more stale
it is. This means that stale species have a lower potential energy than !nstale
species"
n some reactions, the products are more stable than the reactants. !he products therefore
have less potential energy than the reactants, and the potential energy of the reacting
species decreases.
"ince the total energy is always conserved, it follows that the kinetic energy of the
species must increase. !he particles thus move faster and the temperature increases.
#eactions in which the products are more stable than the reactants thus involve a transfer
of energy from potential to kinetic and an increase in temperature.
$E %E
"uch reactions give out heat and are thus said to be E#$THE%&'C.
n other reactions, the reactants are more stable than the products. !he products therefore
have more potential energy than the reactants, and the potential energy of the reacting
species increases.
"ince the total energy is always conserved, it follows that the kinetic energy of the
species must decrease. !he temperature of the system thus decreases. #eactions in which
the reactants are more stable than the products thus involve a transfer of energy from
kinetic to potential and a decrease in temperature.
%E $E
"uch reactions absorb heat and are said to be EN($THE%&'C.
&. "tandard enthalpy changes
!he change in chemical potential energy during a chemical reaction is known as the
enthalpy change for that reaction. t is given the symbol H.
'y convention, if the reaction is exothermic (ie heat is given out) the enthalpy change is
said to be negative* H + ,ve. f the reaction is endothermic (ie heat is absorbed) the
enthalpy change is said to be positive* H + -ve.
!he enthalpy change of a reaction depends on the reaction conditions. t is therefore
necessary to specify standard conditions for the measurement of enthalpy changes. !hese
are taken to be atmospheric pressure (1 atm) and room temperature (&./%). Enthalpy
changes measured under standard conditions are known as stan)ar) enthalpy changes
and are given the symbol H
o
. 0uring these chemical changes, the pressure should be
kept constant.
The enthalpy change for a reaction is the heat energy change meas!re) !n)er
con)itions of constant press!re.
The stan)ar) enthalpy change for a reaction is the heat energy change meas!re)
!n)er stan)ar) con)itions* +,, -Pa an) a state) temperat!re .!s!ally /0123.
!he enthalpy change also depends on the amount of substance used. t is therefore
necessary to specify the amount of reactants used. Enthalpy changes are conventionally
measured in k1mol
,1
.
"o H + heat energy change2no. of moles
3iven a reaction* 4 - 5' &6 - 70
!he standard enthalpy change for this reaction is taken to be the enthalpy change under
standard conditions when one mole of 4 reacts with three moles of ' to give two moles
of 6 and four moles of 0.
Eg f 8.& moles of 4 react with 8.9 moles of ' and &88 k1 of energy are released, the
enthalpy change is &8828.& + ,1&88 k1mol
,1
5. "tandard enthalpies of formation and combustion
!he term :standard enthalpy of reaction: can be used to describe any chemical reaction,
but there are some important reactions which have special names*
!he stan)ar) enthalpy of formation of a substance is the enthalpy change when one
mole of that substance is formed from the most stable allotropes of its elements in their
standard states under standard conditions.
t is given the symbol H
o
f
.
Eg 6(s) - &H
&
(g) 6H
7
(g), H + ,;7./ k1mol
,1
.
!he standard enthalpy of formation of methane is ,;7./ k1mol
,1
.
Eg H
&
(g) - 12&<
&
(g) H
&
<(l), H + ,&/=./ k1mol
,1
!he standard enthalpy of formation of water is ,&/=./ k1mol
,1
.
Eg >
&
(g) - &H
&
(g) - 52&<
&
(g) >H
7
><
5
(s), H + ,59=.9 k1mol
,1
!he standard enthalpy of formation of ammonium nitrate is ,59=.9 k1mol
,1
.
Eg 12&>
&
(g) - 12&<
&
(g) ><(g), H + -/&.8 k1mol
,1
!he standard enthalpy of formation of nitrogen monoxide is - /&.8 k1mol
,1
.
The stan)ar) enthalpy of formation of all elements in their stan)ar) states is 4ero"
!he stan)ar) enthalpy of com!stion of a substance is the enthalpy change when one
mole of that substance is burned in an excess of oxygen under standard conditions.
t is given the symbol H
o
c
.
Eg H
&
(g) - 12&<
&
(g) H
&
<(l), H + ,&/=./ k1mol
,1
!he standard enthalpy of combustion of hydrogen is ,&/=./ k1mol
,1
.
Eg 6H
7
(g) - &<
&
(g) 6<
&
(g) - &H
&
<(l), H + ,/.8.5 k1mol
,1
!he standard enthalpy of combustion of methane is ,/.8.5 k1mol
,1
.
Eg 6
&
H
=
<H(l) - 5<
&
(g) &6<
&
(g) - 5H
&
<(l), H + ,159;.5 k1mol
,1
!he standard enthalpy of combustion of ethanol is ,159;.5 k1mol
,1
.
'urning a substance in oxygen is almost always exothermic, so standard enthalpies of
combustion almost always have negative values.
S!stances which )o not s!pport com!stion, li-e water, caron )io5i)e an) most
other o5i)es, have 4ero enthalpy of com!stion"
7. 6alculating enthalpy changes from temperature changes
Enthalpy changes are generally measured by carrying out a reaction under controlled
conditions in a laboratory and measuring the temperature change.
!he amount of heat required to change the temperature of a system by 1% is known as the
heat capacity of a system (H
c
). t is measured in 1%
,1
.
!he heat energy change for a given reaction can therefore be calculated from the
equation*
q + ! x H
c
.
!he specific heat capacity .c3 is the amount of heat required to heat 1g of a substance by
1%. "o* heat capacity + specific heat capacity x mass
?ass + volume x density
"o* heat capacity + specific heat capacity x volume x density
q + @Ac!
or q + mc!
f a reaction is taking place in solution (and therefore water is the main species present) it
is reasonable to assume that the solution behaves as if it were pure water.
!he density of water is 1.8 gcm
,5
and the specific heat capacity of water is 7.1/ 1g
,1
%
,1
.
"o the calculation is q + (volume of solution) x 7.1/ x !. !he enthalpy change can then
be calculated by dividing the energy change by the number of moles of reactants.
f the temperature goes up the enthalpy change is negative. f the temperature goes down
the enthalpy change is positive.
&EAN 6$N( ENTHALP'ES
0uring a chemical reaction, the bonds in the reactants are broken. !his is an endothermic
processB energy is required to do this. 4fter the bonds have been broken, however, the
bonds in the products are formed. !his is an exothermic processB energy is released when
this happens.
!he enthalpy change for a chemical reaction can be deduced from consideration of the
energy required to break bonds in the reactants and the energy released when the bonds in
the products are formed. t can be calculated from the following equation*
H + Energy required to break bonds in reactants , Energy required to break bonds in
products.
!his method can be used to calculate the enthalpy changes for any reaction which does
not involve ionic bonds. !he breaking and making of ionic bonds involves a more
complicated sequence of energetic processes and thus cannot be considered in this way.
a) ?olecules in the gaseous state
n gas phase reactions, the bonds which are broken and formed are covalent bonds. !he
energy required to separate completely the atoms in one mole of covalent bonds is known
as the on) )issociation enthalpy of that bond (H
b
).
4,'(g) 4(g) - '(g)
'ond H 2k1mol
,1
6,H -715
<,H -797
6,6 -57;
6+6 -91&
6+< -/8=
H,C -=9/
H,6l -75&
6l,6l -&75
'r,'r -1.5
<+< -7./
!hese bond enthalpies are mean valuesB the exact strength of a bond depends on its
environment. Even the strengths of the same type of bond in the same molecule may
vary*
Eg in water* H,<,H(g) H,<(g) - H(g)B H + -=8& k1mol
,1
H,<(g) H(g) - <(g)B H + -7&; k1mol
,1
t is necessary therefore to take an average + ie (=8& - 7&;)2& + -79= k1mol
,1
.
!hus bond enthalpies calculated from different reactions may vary slightly. !hey also do
not take intermolecular forces into account. &ean on) enthalpies th!s only give yo!
appro5imate val!es for enthalpy changes.
b) "olids and liquids
n giant covalent substances, all the covalent bonds have to be broken before free gaseous
atoms can be formed.
n either case, the energy required to separate completely the atoms in one mole of the
substance is known as the atomisation energy (H
at
).
?(s) ?(g), or 4
x
'
y
(s) x4(g) - y'(g)
"ubstance H
at
2k1mol
,1
6(s) 6(g)
-;1;
"i(s) "i(g)
-5;;
"i<(s) "i(g) - &<(g)
-1/97
7sing mean on) enthalpies to calc!late appro5imate enthalpy changes*
!he approximate enthalpy change can be calculated by considering the mean bond
enthalpies of the bonds broken and bonds formed
Eg 6onsider the combustion of methane*
6H
7
(g) - &<
&
(g) 6<
&
(g) - &H
&
<(l)
C
H
H
H
H
O O
C O O
O
H H
+
O O
+
O
H H
'roken* 7 6,H bonds, & <+< bonds* total energy + (7 x 715) - (& x 7./)
+ -&97/ k1mol
,1
Cormed* & 6+< bonds, 7 <,H bonds* total energy + (& x /8=) - (7 x 797)
+ -5799 k1mol
,1
"o approximate DH + &97/ E 5799 + ,/1/ k1mol
,1
!his answer is only approximate because it is using mean bond enthalpies, not molecule,
specific ones, and because it is ignoring changes in intermolecular forces. !he correct
value of DH for the reaction is ,/.8 k1mol
,1
.
(etermining mean on) enthalpies from given )ata*
f the enthalpy change for a reaction is known, and most of the bond enthalpies are
known, it is possible to calculate the mean bond enthalpy of a particular bond*
Eg !he enthalpy of formation of methane is known to be ,;9 k1mol
,1
. !he bond enthalpy
of a H,H bond is -759 k1mol
,1
, and the enthalpy of atomiFation of carbon (6(s) 6(g))
is -;15 k1mol
,1
.
Gsing this information, the mean bond enthalpy of a 6,H bond can be calculated.
6(s) - &H
&
(g) 6H
7
(g)
!he bonds broken are the bonds in carbon (6(s) 6(g)) and & H,H bonds*
!otal energy + ;15 - &(759) + 1=/=
!he bonds formed are four 6,H bonds*
!otal energy + 7x (x + mean 6,H bond enthalpy)
"o 1=/= E 7x + ,;9
"o 7x + 1=/= - ;9 + 1991 k1mol
,1
"o x + 71= k1mol
,1
+ mean bond enthalpy of 6,H
HESS8 LA9
Hess8 Law states that :the enthalpy change for a chemical reaction )epen)s only on
the initial an) final states an) is in)epen)ent of the path followe):.
n other words whichever route, however direct or indirect, by which the reaction
proceeds, the overall enthalpy change for the reaction will be same. t is an application of
the principle of conservation of energy.
HessH Iaw can be used to calculate many enthalpy changes which cannot be measured
directly.
?any enthalpy changes can be calculated simply by using enthalpies of formation and
combustion and applying HessH Iaw.
1. 6alculations using enthalpies of formation
6onsider the reaction 6H
7
(g) - 'r
&
(l) 6H
5
'r(g) - H'r(g)
<ne way by which this reaction could proceed would be to convert all the reactants into
their constituent elements in their standard states and then to convert the elements into
products.
"ince the enthalpy of formation of 6H
7
is ,;7./ k1mol
,1
then the enthalpy change when
one mole of 6H
7
is converted into its elements will be -;7./ k1mol
,1
. 3iven that the
enthalpies of formation of 6H
5
'r and H'r are ,5;.& k1mol
,1
and ,59.7 k1mol
,1

respectively, then the enthalpy change for the reaction by this route can be calculated*
-74.8
+74.8
-37.2
-36.4
CH
4
(g) CH
3
Br(g) HBr(g) Br
2
(g)
+ +
C(s) 2H
2
(g) Br
2
(g)
+ +
4n energetic cycle such as this is known as a HessH Iaw cycle.
H + ,(,;7./) - (,5;.&) - (,59.7) + -1.& k1mol
,1
!he enthalpy change of any reaction can be calculated if the enthalpies of formation of all
the reactants and products are known. !he enthalpy of formation of elements in their
standard states is always Fero.
!he calculation can be condensed into a simple formula*
:H ; <=:H
f
.pro)!cts3> ? <=:H
f
.reactants3>
&. 6alculations using enthalpies of combustion
4ll organic compounds burn in air to give carbon dioxide and water.
6onsider the reaction 6(s) - &H
&
(g) 6H
7
(g)
<ne way by which this reaction could proceed is to convert the reactants to carbon
dioxide and water by combustion, and to convert carbon dioxide and water to methane
and oxygen (ie the reverse of combustion).
f the enthalpy of combustion of methane is ,/.8 k1mol
,1
, then the reverse must be -/.8
k1mol
,1
. !he enthalpy of combustion of hydrogen needs to be doubled because there are
two moles of hydrogen in the equation.
f all the relevant enthalpies of combustion are known, the enthalpy change of the
reaction by this route can be deduced.
C(s) 2H
2
(g)
CH
4
(g)
(+O
2
(g))
(+O
2
(g))
+
CO
2
(g)
2H
2
O(l)
+
-394
(-286 x 2)
(+2O
2
(g))
-890
+890
H + ,5.7 - (& x ,&/9) , (,/.8) + ,;9 k1mol
,1
!he enthalpy change for a reaction can always be calculated if the enthalpy of
combustion of reactants and products are known.
!he calculation can be condensed into a simple formula*
:H ; <=:H
c
.reactants3> ? <=:H
c
.pro)!cts3>