Introduction to thermochemistry

INTRODUCTION TO THEMOCHEMISTRY

Thermo-chemistry is the study of heat energies involved in reactions. This

provides important information regarding heat balances and fuel requirements
in metallurgical processes and is important in theoretical studies.

Every known chemical reaction involves energy changes. In a lot of cases the
heat changes are too small to be obvious. No noticeable changes in
temperature of the surroundings occur. A good example is rusting of metals.

Some reactions evolve heat (give off) and are termed exothermic. Some
reactions absorb heat (take in) and are called endothermic. In exothermic
reactions the system gives out heat to the surroundings. The heat is given a
negative sign. For an endothermic reaction the system absorbs heat from the
surroundings, the heat is given a positive sign, . e.g.

2Al(s) + 3/2 O2(g) (298) ⎯

⎯→ A12O3(s),  H = -1700kJ/mol exothermic
⎯→ Zn (g) + CO(g),  H = +350kJ/mol endothermic
ZnO (s) + C(s)(1373) ⎯

Most metallurgical processes are carried out at constant pressure. Therefore

this study is restricted to heats involved in these reactions at constant pressure,
qp, which is equal to change in enthalpy  H.
The heat changes are given the general name “heats of reaction”, but it is
more convenient to classify them and refer to them as any of the specific ones,
e.g. of formation, of combustion, of fusion, of neutralization, of solution, etc,
according to the type of reaction involved. Accordingly, the word heat may
be replaced with the word ‘enthalpy’.

Definitions

Heat of reaction: This is the change of enthalpy (heat absorbed or evolved)

when the quantities of the reactants stated in an equation
expressed in moles react (together) completely

3Fe2O3 + CO = 2Fe3 O4 + CO2 ;  H 298 = -46700J /mol

Heat of combustion: the change of enthalpy when one mole of a given

substance is burnt completely in oxygen. e.g

C(s) +O2 (g) = CO2(g) ;  H = -393.7 K/Jmol’

CH4 + 2O2(g) = CO2 + 2H2O ;  H = -890 k/Jmol

Heat of formation of a compound: the change of enthalpy when one mole of a

compound is formed from its elements under standard
conditions

C (graphite) + O2(g) = CO2(g)  Ho = -393 K J mol-1,

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 Introduction to thermochemistry

This is the enthalpy of formation for CO2 . This may also be written as

 Ho f298 [CO2 (g)] = -393 kJ mol-1

Examples:

H 2(g) + 1/2 O2(g) = H2O(1)  Hof298 = - 288 KJmol-1

Ca(s) +1/2O2(g) = CaO(S),  Hof298 = -637KJmol-1

Subscript f standing for ‘formation’

Heat of transformation  Hotrans: the enthalpy change occurring when one

mole of a substance undergoes a specific physical change e.g
melting, evaporation, allotropic transformation etc. under standard
conditions. Generally this is given the symbol Lt, but is commonly
described according to the transformation taking place as above. e.g

⎯→ Zn (l) ;  Ho trans .693 = Lt = Lf = +7.14 kJmol-1

Zn (s) ⎯

Trans = transformation
Lt = enthalpy of transformation
Lf = enthalpy of fusion

They all mean the same but Lf is better descriptive of the transformation and is
used. Lf is called the latent heat of fusion.

Zn (1) Zn(g) ;  Ho trans 1180 = Lt = Le = 114.7 KJ mol-1

Le is the molar latent heat of evaporation

C(diamond) C graphite,  Ho trans 2273 = - 2.0 KJ mol-1

Ti (α, hcp) Ti (ß, bcc)  Ho trans 1153. = +3.36 KJ mol-1

These last two are allotropic transformations.

Heat of solution: The change in enthalpy when one mole of a solute is dissolved
in a given amount of solvent, under standard conditions
e.g

NaCl(S) + 200H2O (1) → Na Cl.200H2O (aq)

 Ho sol = + 4.26KJ/mol

Heat of dilution  Ho dil:

The enthalpy change when further solvent is added to a solution of
specific concentration under specific conditions. As solutions are
further diluted the enthalpy changes become progressively smaller. At

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 Introduction to thermochemistry

infinite dilution the ions from the original solute are so widely
separated as free ions in solution that they can no longer interact.

Heat of neutralization  Honeut : The enthalpy change when an acid and a base
react together to give one mole of water

Hess’s law : This may be stated as Hess’s law of constant heat summations.
The change in any state function between two states is constant and
independent of the path taken between the states. Hess’s law states that the
enthalpy change for a reaction is the same whether it takes place in one or
several stages. This is useful for calculation of enthalpy changes for reactions
which can not be carried out experimentally. e.g.
1
C(s) + /2 O2 (g) = CO(g) -1

 Ho for this reaction is not easily determined because of the tendency for
CO2 to form also. Therefore the  Ho, for the reactions below are
experimentally obtained.

C(s) + O2(g) ⎯
⎯→ CO2(g),  Ho2 = -393KJ/mol -2

CO(g) + 1/2O2(g) ⎯
⎯→ CO2(g),  Ho3 = -284KJ/mol -3

C(s) + O2(g) = CO2(g),  Ho2 = -393KJ/mol

(-1) (CO(g) + 1/2O2 = CO2 (g) ),  Ho3 = -284 KJ/mol

------------------------------------------------------------------------------
C(S) + ½ O2 = CO (g)  Ho1 = -109 KJ/mol

In rigorous treatments, errors in the  Ho values must be considered so that the

final value can be viewed in a more accurate light

Heat capacities and Kirchoff’s equation:

Heat capacity at constant pressure is

q p
Cp =
T

 H 
But C p =   ; H is a function of both T and V, but P is constant
 T  p

Heat capacities depend on temperature, and although attempts are made to

explain this dependence, the results of experimental determinations are
expressed in empirical relationships of the type,

Cp = a + bT + cT-2

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 Introduction to thermochemistry

a, b and c are constants determined for a substance over a particular

temperature range. These constants are listed in thermochemical listings such
as those in kubaschweski and Alcock, JANAF etc. curves of variations of
heat capacity can be plotted such as in the following figure.

Enthalpy changes are temperature dependent since they are related to heat
capacities. In changing from state A to B, then

 H = HB - HA

At constant P,

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 Introduction to thermochemistry

  (H )   H B   H A 
 T  =   -  
 P  T  p  T  p
 H 
But   = Cp
 T  p

  (H ) 
 T  = Cp(B) – Cp(A) =  Cp
 P

 Cp is the difference between the heat capacity of the system in its final state
and in its initial state at constant pressure. This is a form of Kirchoff’s
equation. integrating
H2 T2

 d (H ) =  H2 -  H1 =  CpdT
H1 T1

 H2 and  H1 are the enthalpy changes at temperature T2 and T1

respectively. If Cp is not constant for the system over the range of
temperatures concerned, then the empirical expression of the type given
before is used.

T2

 (a + bT CT
−2
 H2 -  H1 = )dT
T1

bT22 bT 2
= (aT2 + - CT −21 ) – (aT1 + 1 - CT 1−1 )
2 2

thus if  H1 is known as in the case of heat evolved in a chemical

reaction,  H2 can be calculated from the known values of Cp

the expression for Cp as given above is applicable in the stated

temperature range over which the value were measured. For example
for Ca which has a low temperature α phase and a high temperature ß
phase and the transition temperature of 737 K, the Cps are given as
follows

α - Ca Cp(s) = 22.2 + 13.9 x 10-3T J/deg mol 298 - 737 K

 - Ca Cp(s) = 6.3 + 32.4x10-3T +10.5x105T-2 J/deg mol 737-1112 K

Ca(l) Cp = 7 1112-1757 K

Heat Content Of Elements

Because the absolute values of H for any state is unknown, only changes in H
can be known. It is a convenient convention to assign a value of zero enthalpy
to elements in their standard states, their most stable states at 298 K (25oC).

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 Introduction to thermochemistry

This means that the enthalpy of a compound at 298 K is equal to the heat of
formation of the compound from its elements at 298 K e.g.

M(S) +1/2O2(g)=MO(S) 298

 Ho298 = HMO(S)298 – HM(S)298 – 1

/2Ho2 298

Because by convention HM298 and Ho2298 are equal to zero then

 H 298 = Hmo298

The variation of heats of reaction or formation with temperature at constant

pressure can be represented on an enthalpy temperature diagram such as given
in the following figure.

Fig: The variation with temperature of the constant pressure heat capacities
of several elements and compounds

Fig: Molar heat content of four substances in their designated states

above 298.15 K and at 1 atm pressure. CaO(c) and Rh(c) are in their normal
standard state of crystalline solid at all temperatures. S2(g) is a non-physical
state below about 882 K and NiO(g) is a non-physical state at all
temperatures.

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 Introduction to thermochemistry

Fig: Molar heat content of zinc above 298.15 K and at 1 atm pressure,
showing discontinuities at the melting and boiling points. The ΔH°m of zinc is
7323 J/mol, and the ΔH°v is 115 330 J/mol.

An example of a non standard enthalpy representation is

 0 298 g ( g ) = + 60.84 kJ/mol

This is because at 298 K and 1 atm Pr, Hg is normally liquid not gas therefore

Hg (1) →  g(g);  o 298 = + 60.8 k/Jmol

Enthalpy Change At Any Temp

The enthalpy change for a reaction at any temperature   can be calculated

if the enthalpy change for the reaction at a specified temperature, usually
298K, is known, and molar heat capacity data are available. The overall
equation is.
T
   = o 298 +  CpdT
298
 Ltrans

 Cp =  Cp PRODUCTS -  Cp REACTANTS

If heat capacities differ in the different states considered, the calculations must
be performed separately.
Tf T2

 =   CpdT  Lf +  CpdT
0 0
2 1 +
T1 Tf

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 Introduction to thermochemistry

Tf and Lf are the fusion (melting) point and latent heat of fusion respectively.
Any other transformation heats must be added appropriately.

Examples:

Calculate the enthalpy change for the following reaction at 298K

2PbS + 3O2 (g) → 2 PbO(s) + 2SO2 (g)

given:  o 298 PbS (s) = -94.5 KJ/mol

 0 298 PbO(s) = -220.5 KJ/mol

0298 SO2 (g) = -298.0 KJ/mol

  =  0 298 =   PROD -   REACT

= 2  298 SO2 + 2  298 PbO - 2  298 PbS - 3  298 O2
 0 298 = 2 (-220.5) + 2(-298.0) - 2(-94.5) - 3 (0)

= - 441 – 596 + 189 – 0 = -848.0KJ

2) calculate o 298 for the following reaction;

3Zn(s) + Al2O3(s) = 2Al(s) + 3 ZnO(s)

 0 298 Al2O3 = - 400.9 KJ/mol

 0 298 ZnO = -83.8 KJ/mol

 0 298 =   298 PROD -   298 REACT

= 3 (-83.8) – (- 400.9) = + 149.5 KJ/mol

3) calculate  0 298 of formation for CS2 (l) given,

CS2(1) + 3O2(g) = CO2(g) +2SO2(g),  0 298 = -1113kJ/mol

C(s) + O2(g) =CO2(g)  0 298 = - 407kJ/mol

S(s) + O2(g) = SO2(g)  0 298 = - 298 kJ/mol

(-1)(CS2(1) +3O2(g) = CO2(g) +2SO2(g)

C(s) + O2(g) = CO2(g)

(2) (S(s) + O2(g) = SO2(g) )

-------------------------------------------------

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 Introduction to thermochemistry

CO2(g) +2SO2(g) + C(s) + O2(g) + 2S(S) + 2O2(g) = CS2(l) + 3O2(g) + CO2(g) +

2SO2(g)

C(S) + 2S(s) = CS2 (1)

 0 298 = (-1)(-1113) + (-407 ) + 2 (-298) = 110 kJ

Example

4) One of the reactions occurring in a copper matte smelting furnace is:

2CaO + SiO2 → 2CaO. SiO2 = Ca2SiO4

Calculate the heat of reaction at 1300oC.

Data

 0 298 CaO = -634.294 kJ/mol

SiO2 = -910.438 kJ/mol

Ca2SiO4 = -136.82 kJ/mol

Cp CaO = 49.62 + 4.519 x 10-3 T – 6.945 x 105T-2 298 - 1973

2xCp CaO = 99.24 + 9.04x 10-3T – 13.05 x105T-2 298 -1973

CpSiO2 = 43.89 + 1.004 x 10-3T – 6.025 x 105T-2 298 - 847

= 60.29 + 8.117 x 10-3T 847 -1973

CpCa2SiO4 = 145.896 + 40.752 x 10-3T – 26.192 x 105 T-2 298 - 970

= 134.557 + 46.108 x 10-3 T 970 -1710

transformation temps + Energies:

SiO2 : 847K

 trans = 1213 J/mol

Ca2SiO4: 970K

 trans = 1841 J/mol

Step 1: calculate o 298

o 298 = o 298PROD - o 298 REACT

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 Introduction to thermochemistry

=  o
298 Ca2SiO4 - 2 o 298 CaO - o 298 SiO2

= (-136.82) – 2(-634.294) – (-910.438) KJ

= -136.82 + 1268.59 + 910.498 KJ

= +2042.206 KJ
 T - o 298 =   CpdT
 T = o 298 +   CpdT

 CpdT 298 - 847

 Cp =  Cp PROD -  Cp REACT

= 145.896 + 40.752 x 10-3T – 26.192 x 105 T-2 – (97.65 +9.04 x 10-3T

–13.05 x105 T-2 + 43.89 + 1.004 X10-3 T – 6.025 x105T-2)

= 4.356 + 30.708 x 10-3 T – 7.1117 x 105T-2

T2 847

 CpdT
T1
= 
298
(4.356 + 30.708 x 10-3T – 7.117 x 105T-2 )dT

847
 30.708 x10−3 T 2 
=  4.356T + + 7.11x105 T −1 
 2  298

= (3698.5 + 11015.1 + 840.26) – (1298.09 + 1363.5 + 2388.3)

= 10494.97 J

 CpdT 847 – 970

Cp = 145.896 + 40.752x10-3T - 26.192x105T-2 - (97.65 + 9.04x10-3T
- 13.05x105T-2 + 60.29 + 8.117x10-3T )
= -12.044 - 23.595x10-3T + 13.142x105T-2
T3 970

 CpdT
T2
=
847
 (-12.044 + 23.595x10-3T + 13.142 x105T-2)dT

970
 23.595 x10−3 T 2 
=  −12.044T + − 13.143x105 T 1 
 2 847

= (− 11682.78 + 1100.27) - (− 10201.3 + 8443.9 − 1551.6) = 1371.67

 CpdT 970 -1573

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 Introduction to thermochemistry

(
Cp = 134.557 + 46.108x10−3 T − 97.65 + 9.04x10−3 T − 13.05x105 T −2 + 60.29 + 8.117x10−3 T )
= - 23.383 + 28.951x10 −3 T + 13.05x105 T −2

T4 1573

 CpdT =  ( −23.383 + 28.951x10 T + 13.05 x105 T −2 )dT

−3

T3 970

1573
 28.951x10−3 T 2 
=  −23.383T + − 13.05x105 T −1  
 2   970

= (-36781.5+35817.1-827.6- -22681.5+27240.0-1345.4) = -5005.1

 T =  0
298 +  CpdT + Lt
= +2042.2KJ + 10494.97 + 1371.67 - 5005.1 – 1213 + 1841 = 2050.32KJ

In this example it should be noted that in a smelting situation, the above

compound will be molten at 1573 K due to the influence of the other oxides in
the charge which effectively drop the melting point of this oxide to as low as
less than 1150oC. In the actual situation, the heat of reaction will be modified
by the effect of the fusion and the temperature lowering effect of the other
oxides.

MAXIMUM FLAME TEMPERATURE

Maximum flame temperature can also be termed ideal flame temperature or

adiabatic flame temperature. Maximum flame temperature can have a wider
meaning than the other two and adiabatic in particular is quite restricted. The
three taken together are understood in this case here to mean the temperature
attainable for a given situation or fuel when it is burned without LOSS of any
of the (energy) heat of combustion to the surroundings. In such a situation it
is implied that combustion occurs in such a way that all the energy is released
as heat: which heat is taken up by the products of combustion instantly. This
precludes heat loss by such modes as radiation etc. Other assumptions made
are as follows:

1. complete oxidation by the exact stoichiometric addition of oxidant i.e.

air or O2 enriched air
2. perfect mixing
3. instantaneous combustion so that no heat losses occur during burning.

To calculate adiabatic flame temperature, the following steps are executed.

1. Total heat content of reactants + Inerts (= Sensible heat (N2 + ash

etc)above room temperature
+ Heat of reaction (=Oxidation = Combustion)
= Heat content of the products

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 Introduction to thermochemistry

Temperature of products =
Total heat
Mass, volume of products  Average heat capacity of products

i.e MC T = q
q
 =
MC

M = mass, Vol of Products

C = Heat Capacity of Products

Example:

Calculate the “ideal” Flame temperature for the combustion of methane by air
preheated to 600oC
Specific heat of air = 0.327 Cal/L/oC. 0 – 2000oC

Specific heat of CO2 = 0.58 “

Specific heat of H2O = 0.46 “
Specific heat of N2 = 0.36 “

Reaction:
CH 4 + 2O2 = CO2 + 2 H 2O :  = -191,800 cal /mole CH4

Considering ambient temperature as 20oC,

Per mole CH4, vol O2 required = 2 x 22.4 liters
= 44.82 liters
44.8
” “ “ “ air required = = 213.15 liters
0.21
N2 Volume = 213.5 - 44.8 = 168.7 liters
Sensible heat in air = 213.5 x 0.324 Cal/L oC x (600 – 20)
= 40027 Cal

Total heat in products of combustion = 191, 800 + 40027

= 231827 Cal
Products per mol of CH4 burnt:
1 mol CO2 = 22.4 L
2 moles H2O = 44.8 L
N2 = 168.7 L
235.9 L
q
Temperature rise = = T
MC
231827
=
22.4  0.58 44.8  0.46 168.8  0.36
235( + + )
235.9 235.9 235.9

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 Introduction to thermochemistry

231827
= = 2456.9 degrees
0.4  235.9
then the ideal flame temperature is:

= 2456.5 + 20 = 2481.9 oC = 2754.9 K

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