You are on page 1of 19

Energy Balances with Reaction

In any chemical reaction, energy is required to break the reactant


bonds and energy is released when the product bonds are formed
The large changes in enthalpy and internal energy during a chemical
reaction necessitates substantial heat transfer (heating or cooling)
from the reactor in order to maintain the reactor at its desired
operating temperature
The net change of enthalpy is called the heat of reaction, and is the
energy that must either be transferred to or from the reactor to
maintain the desired reactor temperature

Heats of Reaction
By definition, the heat of reaction, r (T,P), is the enthalpy change for a
process in which stoichiometric quantities of reactants at temperature T
and pressure P react completely to form products at the same
temperature and pressure.
For the following reaction,

aA + bB cC + dD
r is calculated as the difference between the product and reactant
enthalpies (at constant T,P) which are weighted by their stoichiometric
coefficients. Therefore,
H (T , P) [kJ/mol] = H
H
r

products

reactants

= cH C (T , P ) + dH D (T , P ) aH A (T , P ) bH B (T , P )
= H (T , P )

Heats of Reaction
The units of r are kJ/mol but, per mole of what?? Recall that the
reported r applies to stoichiometric quantities of each species. For
example,
2A + B 3C
r (100C, 1 atm) = -50 kJ/mol
the enthalpy change for the given reaction is
50 kJ
50 kJ
50 kJ
=
=
2 mol A consumed 1 mol B consumed 3 mol C generated

If 150 mol of C/s was generated at 100C and 1 atm,

150 mol C generated


50 kJ

H& =
= 2500 kJ/s
s

3 mol C generated

Heats of Reaction Extent of Reaction


In general, if nA,r moles of A are generated or consumed by reaction at a
temperature T and pressure P and A is the stoichiometric coefficient of
the reactant or product, the associated enthalpy change is:

H r (T , P )
&
H =
n A, r = &H r (T , P )
|A |

Recall that the extent of reaction, , is a measure of how far a reaction


has proceeded.
| (n& A )out (n& A )in | | n A, r |
&
=
=
| A |
| A |

Notes on Heats of Reaction


1. If r (T,P) is negative, the reaction is exothermic energy must be
removed from the reactor to keep the temperature from increasing
2. If r (T,P) is positive, the reaction is endothermic energy must be
added to the reactor to keep the temperature from decreasing
3. At low and moderate pressure, r (T,P) is nearly independent of
pressure. Therefore, r (T,P) r (T)
4. The value of the heat of reaction depends on how the stoichiometric
equation is written. For example:
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(l): r1 (25C) = -890.3 kJ/mol
2 CH4(g) + 4 O2(g) 2 CO2(g) + 4 H2O(l): r2 (25C) = -1780.6
kJ/mol

Notes on Heats of Reaction


5. The value of the heat of reaction depends on the phase of the
reactants and products. For example:
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(l) : r1 (25C) = -890.3 kJ/mol
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g) : r2 (25C) = -802.3 kJ/mol
6. The standard heat of reaction, r, is the heat of reaction when
both reactants and products are at standard conditions, 25C and
1 atm.
The symbol denotes standard conditions (i.e., 25C and 1 atm).

Example
1. The standard heat of the combustion on n-butane vapour is

C 4H10 (g) +

13
O 2 (g) 4 CO 2 (g) + 5 H2O(l)
2

H ro = 2878 kJ/mol

Calculate the rate of enthalpy change, H& (kJ/s) if 2400 mol/s of CO2 is
produced in this reaction and the reactants and products are all at 25C.
2. The heats of vapourization of n-butane and water at 25C are 19.2 kJ/mol
and 44.0 kJ/mol, respectively. What is the standard heat of the reaction

C 4H10 (l) +

13
O 2 (g) 4 CO 2 (g) + 5 H2O(v)
2

Calculate H& if 2400 mol/s of CO2 is produced in this reaction and the
reactants and products are all at 25C.

Closed System Reactions


What if the reaction takes place in a closed system of constant volume?
Energy balance:

U + Ek + Ep = Q W

The internal energy of reaction, r (T), is calculated as the difference


between the product and reactant internal energies if stoichiometric
quantities of reactants react completely at temperature T.
U (T ) = U
U
r

products

reactants

Assuming ideal gas behaviour, the internal energy is related to the heat
of reaction by

| vi |
| vi |
U r (T ) = H r (T ) RT

gaseous
gaseous

products
reac tan ts

where I is the stoichiometric coefficient of the ith gaseous reactant or


product. (See F&R Ex. 9.1-2)

Measurement of Heats of Reaction


Heats of reaction are measured in a calorimeter. A calorimeter is a
closed reactor that is submersed in a fluid and enclosed in an insulated
vessel. The increase or decrease in fluid temperature determines the
amount of energy released or absorbed and using the heat capacities of
the reactants and products, H r can be determined.
However, this measurement technique will not work for every reaction.
For example, consider the following reaction:
1
H r (25C, 1 atm) = ?
C(s) + O 2 (g) CO(g)
2
- only minimal amounts of CO would form since the rate of reaction
at 25C is too low
- higher reaction temperatures (higher reaction rates) would not
lead to the formation of pure CO but rather a mixture of CO and
CO2

Measurement of Heats of Reaction


What if we cant measure experimentally H r for our desired reaction?
1
H r1 = ?
C + O 2 CO
2
However, we can measure these heats of reaction,
H = 393.51 kJ/mol
C + O CO
2

CO +

C+

r2

1
O 2 CO 2
2

1
1
O2 (+ O2 )
2
2

H r3 = 282.99 kJ/mol
H r1

H r = H r2

1
CO( + O 2 )
2
H r = H r3

CO 2
H r1 = H r2 + ( H r3 ) = -393.51 + (-282.99) = -110.52 kJ/mol

Hesss Law
The previous result could be more readily obtained if we treated the
stoichiometric equations as algebraic equations. That is,

1
C + O 2 CO O 2 CO 2 CO 2 (reaction 2 - reaction 3)
2

1
C + O 2 CO (desired reaction 1)
2
H r1 = H r2 H r3 = 393.51 ( 282.99) = -110.52 kJ/mol

Hesss Law if a set of reactions can be manipulated through a series


algebraic operations to yield the desired reaction, then the desired heat
of reaction can be obtained by performing the same algebraic
operations on the heats of reaction of the manipulated set of reactions

Example
The standard heats of the following combustion reactions have been
determined experimentally:

7
O 2 2 CO 2 + 3 H2O
2
C + O 2 CO 2
1
H2 + O 2 H2 O
2

C 2H6 +

H r1 = 1559.8 kJ/mol
H r2 = 393.5 kJ/mol
H r3 = 285.8 kJ/mol

Use Hesss Law and the given heats of reaction to determine the
standard heat of the reaction
2 C + 3 H2 C 2H6

H r4 = ?

Calculating r from Heats of Formation


The H r can be calculated using standard heats of formation. A
formation reaction of a compound is the reaction in which the compound
is formed from its elemental constituents as they would occur in nature
(e.g., O2 rather than O).
The enthalpy change associated with the formation of 1 mole of the
compound at 25C and 1 atm is the standard heat of formation H f of
the compound. H f for many compounds are found in Table B.1.
For example, from Table B.1 it can be seen that the H f of ammonium
nitrate (NH4NO3(s)) is -365.14 kJ/mol. This signifies that,
3
N2 (g) + 2 H2 (g) + O 2 (g) NH4NO 3 (s)
2

H r = 365.14 kJ/mol

Calculating r from Heats of Formation


A consequence of Hesss Law is that the H r of any reaction can be
calculated as:

H r =

vi H f i =

| vi | (H f ) i

products

| vi | ( H f ) i

reactants

where,

i is the stoichiometric coefficient of reactant or product species i


(H f ) i is the standard heat of formation of species i
The standard heats of formation of all elemental species
(e.g., O2, N2, Zn, etc.) are zero.

Example
Determine the standard heat of reaction for the combustion of liquid npentane.
C5H12(l) + 8 O2(g) 5 CO2(g) + 6 H2O(l)

Calculating r from Heats of Combustion


The standard heat of combustion of a species, H c, is the enthalpy
change associated with the complete combustion of mole of a species
with oxygen at 25C and 1 atm such that:
all the carbon forms CO2(g)
all the hydrogen forms H2O(l)
all the sulphur forms SO2(g)
all the nitrogen forms N2(g)
H c values for combustible species (if available) are found in Table B.1.

For example, from Table B.1 it can be seen that the H c of ethanol is
-1366.9 kJ/mol. This signifies that,

C 2H5 OH(l) + 3 O 2 (g) 2 CO 2 (g) + 3 H2O(l)

H r = 1366.9 kJ/mol

Calculating r from Heats of Combustion


A consequence of Hesss Law is that the H r of any reaction involving
only oxygen and a combustible species can be calculated as:
H r =

v (H
i

where,

c )i

| v | (H
i

reactants

c )i

| v | (H
i

c )i

products

Note: this is reverse to determining the


heat of reaction from heats of formation

i is the stoichiometric coefficient of reactant or product species i

(H c ) i is the standard heat of formation of species i

If any reactants or products are combustion products (i.e, CO2,


H2O(l), SO2,), their heats of combustion are zero.

Example
Calculate the standard heat of reaction form the dehydrogenation of
ethane:
C2H6 C2H4 + H2

Determining f from c
For many substances, it is much easier to measure H c than H f
For example, the formation of pentane:

5 C(s) + 6 H2 (g) C 5H12 (l)

H f = ?

Carbon, hydrogen and pentane can all be burned and their standard
heats of combustion determined experimentally. Therefore,

( H f )C5H12 (l) = 5( H c )C(s) + 6( H c )H2 (g) - ( H c )C5H12 (l)