CHEMISTRY GRADE 12

Some Properties of Enthalpy

1. Enthalpy is an extensive property. The enthalpy of a system depends on the quantities
of substances present. Consider the formation of ammonia from nitrogen and
hydrogen;

1/2N2(g) + 3/2H2(g) U NH3(g); ∆Hf = –45.9 kJ/mol

It is found experimentally that –45.9 kJ of heat is produced when 1/2 mole of

nitrogen reacts with 3/2 moles of hydrogen to produce 1 mole of ammonia at constant
pressure system.

1 mole of nitrogen reacts with 3 moles of hydrogen to form 2 moles of NH3 and
– 91.8 kJ of heat is produced.

2. The enthalpy change for a reaction is equal in magnitude but opposite in sign to DH
for the reverse reaction. For example, if we assume for the reverse reaction of the
formation of ammonia (forward reaction for decompostion of ammonia):

NH3(g) U 1/2N2(g) + 3/2H2(g); ∆Hr = +45.9 kJ/mol

1/2N2(g) + 3/2H2(g)

DHr = +45.9 kJ DHf = –45.9 kJ

NH3(g)

Figure 3.4 Reversing a reaction changes the sign but not the magnitude of the
enthalpy change: DHr = – DHf .

3. The enthalpy change for a reaction depends on the state of the reactants and the
products. If the product in the combustion of methane were gaseous H2O instead of
liquid H2O, DH would be – 802 kJ instead of – 890.3 kJ. This is due to the absorption
of 88 kJ of heat when 2 mol of liquid water is changed to gaseous water.

2H2O(l) Æ 2H2O(g); ∆H = + 88 kJ

Therefore, the states of the reactants and products must be specified.

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3.3.2 Standard States

Is there any difference between standard states of ideal gases and standard states
of thermodynamic properties?
The standard state for a substance is the most stable form at temperature of 25°C and at
atmospheric pressure of 1 atm. We can define the standard enthalpy of combustion, DH°C,
as the change in enthalpy that accompanies the combustion of 1 mole of a substance in
oxygen at standard conditions. Most chemical reactions that produce heat are combustion
reactions. The food we eat is combusted in our bodies in order to give us energy. Most of
the energy our bodies need comes from carbohydrates and fats. Carbohydrates are
decomposed in the intestines into glucose, C6H12 O6.
Glucose is soluble in blood and is known as blood sugar. It is transported by the blood to
cells, where it reacts with O2 in a series of steps, eventually producing CO2(g), H2O(l),
and energy.

C6H12O6(s) + 6O2(g) Æ 6CO2(g) + 6H2O(l); ∆H C° = – 2816 kJ

The breakdown of carbohydrates is rapid, so their energy is quickly supplied to the body.
Standard Enthalpies of Formation
The standard enthalpy of formation, ∆H f° , is the change in enthalpy in the reaction when
one mole of a substance is formed from the elements in their standard states. By definition,
the standard enthalpy of formation of the most stable form of any element is zero.
Table 3.2 Standard enthalpies of formation, ∆Hf° , of some substances at 25°C.

Substance Formula ∆Hf° (kJ/mol)

Acetylene C2H2(g) 226.7
Ammonia NH3(g) – 46.11
Benzene C6H6(l) 48.99
Calcium carbonate CaCO3(s) – 1207.1
Calcium oxide CaO(s) – 635.5
Carbon dioxide CO2(g) – 393.5
Diamond C(s) 1.88
Ethane C2H6(g) – 84.68
Ethanol C2H5OH(l) – 277.7
Ethylene C2H4(g) 52.26
Glucose C6H12O6(s) – 1260

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Substance Formula ∆Hf° (kJ/mol)

Hydrogen bromide HBr(g) – 36.23
Hydrogen chloride HCl(g) – 92.30
Hydrogen fluoride HF(g) – 271.1
Hydrogen iodide HI(g) 26.48
Methane CH4(g) – 74.85
Methanol CH3OH(l) – 238.6
Nitric oxide NO(g) 90.25
Nitrous oxide N2O(g) 82.05
Nitrogen dioxide NO2(g) 33.18
Propane C3H8(g) – 103.85
Silver chloride AgCl(s) – 127.0
Sodium bicarbonate NaHCO3(s) – 947.7
Sodium carbonate Na2CO3(s) – 1130.9
Sodium chloride NaCl(s) – 441.0
Sulfur dioxide SO2(g) – 296.8
Sulfur trioxide SO3(g) – 395.7
Water H2O(l) – 285.8
Water vapor H2O(g) – 241.8

Now let us explore how we can use standard enthalpies of formation to determine standard
enthalpy changes of chemical reactions.
We sum the enthalpies of formation of all reaction products, taking care to multiply each
molar enthalpy of formation by the coefficient of that substance in a balanced equation.
From this, we subtract a similar sum of the enthalpies of formation for the reactants:

= ∑ n∆H f°( products ) – ∑ m∆H f ( reactants )

° °
∆H rxn

where, n and m are the stoichiometric coefficients of the chemical reaction.

Example 3.4
The standard enthalpies of formation of NH3, H2O and NO are –46.2, –241.8
and 90.3 kJ/mol, respectively. Calculate the enthalpy of the reaction:
4NH3 (g) + 5O2 (g) Æ 6H2O(l) + 4NO (g)

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Solution:
The convenient way to begin this kind of calculation is to list ∆H f° under the
formula of each substance in the equation.
4NH3 (g) + 5O2 (g) Æ 6H2O (l) + 4NO (g)
–46.2 kJ 0 –241.8 kJ 90.3 kJ
Now we can multiply these ∆H f° values by the numbers of moles given by the
coefficients in the equation. In substituting these values into the general equation for
∆H f° , remember that we must subtract the sum of the terms for the reactants from
the sum of the terms for products.
°
∆H rxn = 6  ∆H f° ( H 2 O )  + 4  ∆H f° ( NO )  – 4  ∆H f° ( NH 3 )  – 5  ∆H f° ( O 2 )

= 6 (–241.8 kJ/mol) + 4 (90.3 kJ/mol) – 4 (–46.2 kJ/mol) – 5 (0 kJ/mol)

= –1450.8 kJ + 361.2 kJ + 184.8 kJ – 0
= –904.8 kJ

Example 3.5
Calculate DH ° for combustion of propane, C3H8, from the ∆H f° values of the
products and reactants.
C3H8 (g) + 5O2 (g) Æ 3CO2 (g) + 4H2O (l)
Solution:

As usual, first we list ∆H f° under the formula of each substance in the equation:
C3H8(g) + 5O2(g) Æ 3CO2(g) + 4H2O(l)
–103.8 kJ 0 –393.5 kJ –285.8 kJ
DHrxn = 3(–393.5 kJ/mol) + 4 (–285.8 kJ/mol) – (–103.8 kJ/mol) – 5(0)
= (–2324) – (–103.8)
= –2220 kJ

Exercise 3.3
1. Using the standard enthalpies of formations given in Table 3.2, calculate the DH °
for the reaction:
CH4 (g) + 2O2 (g) Æ CO2 (g) + 2H2O (l)

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2. Compare the quantity of heat produced by combustion of 1.00 g of propane,

C3H8, with that produced by 1.00 g of benzene, C6H6. (Hint: refer to Example
3.5, above).

The standard molar enthalpy of neutralization is the change in enthalpy, DHneut, when
one mole of an acid or a base is completely neutralized. For example, the heat of
neutralization for
HCl(aq) + NaOH(aq) Æ NaCl(aq) + H2O(l) DHneut= –56.2 kJ/mol

Example 3.6
1.00 × 102 mL of 0.5 M HCl was mixed with 1.00 × 102 mL of 0.5 M NaOH. The
initial temperature of the HCl and NaOH solution was the same, i.e., 22.5°C, and
the final temperature of the mixed solution was 25.86°C. Calculate the heat change
for the neutralization reaction on a molar basis.
NaOH(aq) + HCl(aq) Æ NaCl(aq) + H2O(l)
Assume that the densities and specific heats of the solutions are the same as for
water (1.00 g/mL, and 4.184 J/g°C, respectively)
Solution:
Assuming no heat lost to the surroundings, qsys = qsoln + qrxn = 0, so qrxn = –qsoln,
where qsoln is the heat absorbed by the combined solution. Because the density of
the solution is 1.00 g/mL, the mass of a 100 mL solution is 100 g. Thus
q
Specific heat =
m × ∆T
qsoln = m × CDT
= (1.00 × 102 g + 1.00 × 102 g) (4.184 J/g°C) (25.86°C – 22.50°C)
= 2.81 × 103 J = 2.81 kJ
Because qrxn = –qsoln, qrxn = –2.81kJ
The number of moles of both HCl and NaOH in 1.00 × 102 mL solution is:
0.5mol
×0.1L = 0.05mol
1L
Therefore, the heat of neutralization when 1.00 moles of HCl react with 1.00

2.81kJ
moles of NaOH is – = –56.2kJ / mol
0.05mol

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