Energetics

D.Hines Chemistry UNIT 1

Enthalpy changes

Enthalpy and enthalpy change

Energy has to be absorbed to separate particles from each other. The heat content is the total amount
of energy (potential and kinetic) in chemicals. The heat content is also called the enthalpy (H). All
chemical reactions require a minimum amount of energy to break bonds of reactant molecules before
new bonds are formed to make products. This is known as the activation energy (Ea).

We cannot measure enthalpy by itself, so therefore we assume that all elements in their normal physical
states at 101325Pa pressure and 298K have zero enthalpy. Solutions involved have a concentration of 1
moldm-3. These conditions are called standard conditions. The symbol 𝛳 is used to show standard
conditions.

However we can measure enthalpy changes, these occur when heat energy is exchanged with the
surroundings in a chemical reaction (△H𝛳).

Enthalpy change = enthalpy of products – enthalpy of reactions

△H𝛳 = △Hproducts - △Hreactants

The units of enthalphy change is kJmol-1

Exothermic and endothermic reactions

Two important terms which are common in chemistry are:

 System – the chemical reactants and products

 Surrounding – these include the air, the container in which a reaction is carried out, any
solvents not taking part in the reaction and anything dipping into the reaction mixture eg
thermometer.

An endothermic reaction absorbs energy from the surroundings. The surroundings decrease in
temperature. The energy of the reactants is the greater than the energy of the products.

△Hproducts - △Hreactants is positive. So △Hreaction is positive (+ve).

All reactions requiring a continuous input of heat are endothermic, e.g thermal decompositions, some
salts dissolve in water. NH4Cl.

An exothermic reaction releases energy to the surroundings. The surroundings increase in temperature.
The vessel gets hotter. The energy of the products is less than that of the reactants.

△Hproducts - △Hreactants is negative. So △Hreaction is negative (-ve).

All combustions are exothermic. Many reactions of metals with acids are exothermic and neutralization
reactions

Energy profile diagrams

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Energy profile diagrams show:

 The relative enthalpy of the reactants and products on the y-axis, this includes the formulae of
reactants and products.
 The reaction pathway on the x-axis

Bond making and bond breaking

 Breaking the bond between two atoms requires energy. It is endothermic.

 Making new bonds between atoms release energy. It is exothermic.
 If the energy absorbed in bond breaking is greater than the energy released in making new
bonds the reaction is endothermic.
 If the energy absorbed in bond breaking is greater than the energy released in making new
bonds the reaction is endothermic.

Bond energies

Bond energy is the amount of energy needed to break one mole of a particular bond in mole of
gaseous molecules. Otherwise known as bond dissociation energy. The symbol is E. the type of bond
broken is put after this symbol.

The units of bond energy are kJmol-1. Eg. E(C=C) = +610 kJmol-1 refers to the energy required to
break a C=C double bond.

Values of bond energies are always positive because they refer to bonds being broken, when bonds
are formed for the same type of bond the amount of energy is the same as the energy absorbed.
However the sign of the value will be negative. For example:

O=O(g) ⟶ 2O(g) △H = + 496 kJ mol-1

2O(g) ⟶ O=O(g) △H = - 496 kJ mol-1

Factors affecting bond energy

 For atoms of the same type of bond, double bonds have higher bond energies than single
bonds. This is because there is greater attractive force between the two bonding pairs of
electrons and the nuclei of the atoms compared to only one bond pair.

E(C-C) = + 350 kJ mol-1 E(C=C) = + 610 kJ mol-1

 The bond energies decrease down the group as the distance between the nuclei increases.
There is less force of attraction between the bonding pair of electrons and the nuclei as the
bond lengthens.

E(Cl-Cl) = +244 kJ mol-1 E(Br-Br) = 193+kJ mol-1 E(I-I) = + 151 kJ mol-1

Also note that the bond energies of carbon-halogen bonds also decrease as the halogen atom increases
in size.

E(C-Cl) = + 340 kJ mol-1 E(C-Br) = + 280 kJ mol-1 E(C-I) = + 240 kJ mol-1

 The bond energy of a particular type of bond can be affected by other atoms in a molecule.
For example:

E(C-F) in CH3F = +452 kJ mol-1 E(C-F) in CF4 = + 485 kJ mol-1

For this reason we often use average bond energies, E. These values are standard and will be given on
data sheets.

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Using bond energy to calculate ∆H

Enthalpy change can be calculated from bond energies. The bond energy is the energy absorbed when a
bond is broken or the energy evolved when a bond is formed. The overall change in energy for bond
breaking and bond forming is calculated as the enthalpy change.

Example 1

Calculate the enthalpy of combustion of methane using the bond energy values shown below.

Bond present Bond enthalpy (kJ mol-1)

C-H +413
O=O +498
C=O +805
O-H +464

The reaction is as follows:

CH4(g) + 2O2(g) → CO2(g) +2H2O(g)

Bonds broken = 4(C-H) + 2(O=O)

= 4(+413) + 2(+498)

= +2648

Bonds formed = 2(C=O) + 4(O-H)

= 2(-805) + 4(-464)

= -3466

∆HC = -818 kJmol-1

Example 2

bond enthalpy (kJ mol-1)

C-H +413

Cl-Cl +243

C-Cl +346

H-Cl +432
Calculate the enthalpy of reaction above

Standard enthalpies

The standard enthalpy of reaction (∆Hϴr) can be defined as the enthalpy change when the mole
quantities shown in the balanced equation react under standard conditions. In cases where the element
exist as allotropes, the most stable form under standard conditions is used as the standard. For example
reactions involving carbon, graphite is used rather than diamond.

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Standard enthalpy of formation (∆Hϴf)

The standard enthalpy of formation is the heat change when one mole of substance is formed from its
constituent elements in their normal state under standard conditions.

 Example the enthalpy of formation of ethanol is written as

∆Hϴf [C2H5OH(l)] = -277 kJ mol-1

The equation is written as 2C(graphite) + 3H2(g) + ½O2(g) → C2H5OH

To balance the equation you must ensure that one mole of ethanol is formed and everything else is
balanced accordingly.

 Similarly, the equation for enthalpy of formation of water is given below:

H2(g) + ½O2(g) → H2O(l) ∆Hϴf [H2O(l)] = -286 kJ mol-1

 Also note that the enthalpy change of an element in its normal physical state is zero and is
used as the reference state of the element. No heat change is involved.

O2(g) → O2(g) ∆Hϴf [O2(g)] = 0 kJ mol-1

Standard enthalpy of combustion ∆HϴC

The standard enthalpy of combustion ∆HϴC is the heat change when 1 mole a substance is completely

burnt in oxygen under standard conditions. The standard enthalpy change of ethane is written as:

∆HϴC [C2H5(g)] = - 1560 kJ mol-1

This represents the equation

C2H6(g) + 3 1/2O2(g) → 2CO2(g) + 3H2O(l), substances must be completely burnt in oxygen to ensure 1 mole

of substance reacts.

Standard enthalpy of neutralization ∆Hϴn

The standard enthalpy of neutralization (∆Hϴn) is the enthalpy change when an acid reacts with a base to

form one mole of water under standard conditions. For example

∆Hϴn [HCl/NaOH (aq)] = - 57.9 kJ mol-1

This represents the equation

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)

Although the balanced equation for the reaction between sulphuric acid and sodium hydroxide is

H2SO4(aq) + 2NaOH(aq) → Na2SO4(aq) + 2H2O(l)

 The standard enthalpy of neutralization for this reaction is – 57.9 kJ mol-1 because it

measures the heat change per mole of water formed.

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  A reaction between a strong acid and strong base will always give an enthalpy of

neutralization of – 57.9 kJ mol-1.

 This is because with strong acids and bases are fully ionized in solution and the common net

ionic reaction that releases heat in all cases is: OH-(aq) + H+(aq) → H2O(l) ∆H = -57.9 kJ mol-1.

Enthalpy of atomization (∆Hϴat)

The standard enthalpy of atomization (∆Hϴat) is the heat change when 1 mole of gaseous atoms is

formed from the element under standard conditions.

Na(s) → Na(g) ∆Hϴat [Na(s)] = + 108 kJ mol-1

½ H2(g) → H(g) ∆Hϴat [H2(g)] = + 218 kJ mol-1

Standard enthalpy change of solution (∆Hϴsoln)

The enthalpy change when one mole of a solute (substance) is dissolved in a very large amount of water

(solvent) to form an infinitely dilute solution under standard conditions.

Example: NaCl(s) + aq → Na+(aq) + Cl-(aq) ∆Hϴsoln = +3.9 kJ/mol

Finding enthalpy changes using a calorimeter

We can calculate many enthalpy changes from the results of experiments involving a calorimeter. A

calorimeter is an insulated container which prevents heat released by a reaction from escaping into the

surface. A calorimeter can be a polystyrene cup, a metal can, a vacuum flask or a more complex piece of

apparatus. The general procedure is:

 React known amounts of reactants in a known volume of solution

 Measure the temperature change of the solution.

 Calculate the energy transferred using the relationship q = mc∆T

Where q is the energy transferred in Joules (J),

m is the mass of solution in the calorimeter in grams (g), it is always the mass of water or mass

of the aqueous solution not the mass of solute added to the solution.

c is the specific heat capacity of water (Jg-1C-1). Value of c = 4.18 Jg-1C-1.

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 ∆T is the temperature change (rise or fall)

 Calculate the enthalpy change per mole of specific reactant for ∆Hϴsoln ,

Assumptions made are:

 Density of water is 1 g/cm3 or 1 g = 1 cm3

 Aqueous solutions are treated as if they are water

 The solution has the same heat capacity as water

 When a solid is added, the mass of the solid is ignored

 There is no heat loss during the reaction.

Example 1

0.9g of zinc was added to 75 cm3 of 0.25 moldm-3 copper (II) sulphate solution in a calorimeter. The

copper(II) sulphate is in excess. The mixture is stirred constantly. The temperature rose from 18 0C to

27.9 0C. Calculate:

(a) The number of moles of zinc added

(b) The energy released

(c) The energy release per mole of solute

(d) Draw an energy diagram to show the reaction that took place

Standard enthalpy change of combustion by calorimetry

A simple apparatus used to measure the enthalpy change of combustion is shown below.

For this procedure we need to know:

 The mass of the water in the calorimeter

 The temperature rise of the water

 The mass of the fuel burnt

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  The molar mass of the fuel

The value of the ∆Hc is calculated per mole of fuel burnt

QUESTIONS

Exercise 1

1. Magnesium will also displace copper from copper (II) sulphate solution. If an excess of

magnesium is added to 100 cm3 of 1.0 moldm-3 copper(II) sulphate, the temperature increases

by 46.3 oC. a) Calculate the molar enthalpy change for the reaction

b) Calculate the minimum quantity of magnesium required to ensure it is in

excess.
c) Calculate the temperature change if only 0.8 g of magnesium is added.

2. When 5.73 g of sodium chloride (NaCl) dissolves in 100 cm3 of water, the temperature of the
water fell from 22.4 oC to 19.8 oC. Calculate the heat change and the enthalpy of solution of the
reaction

3. If 50 cm3 of 1.0 moldm-3 NaOH is added to 25 cm3 of 2.0 moldm-3 CH3COOH, the temperature
rose by 8.3 oC. Calculate the molar enthalpy change for the reaction.

EXERCISE 2 - bond dissociation enthalpies

1. Given the following data:

bond Hb/kJmol-1 bond Hb/kJmol-1

C-H +413 H-F +565

C-Br +280 C-F +425

H-Br +366 F-F +158

Br-Br +193 C=O +805

C-C +347 O-H +464

C=C +611 O=O +498

H-H +435

Substance Hat/kJmol-1

C(graphite) +713

Calculate:

a) The H for the following reaction: CH4(g) + Br2(g)  CH3Br(g) + HBr(g)

b) The enthalpy of formation of HF
c) The enthalpy of formation of propene

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d) The enthalpy of formation of 1,2-dibromopropane
e) The enthalpy of combustion of ethane

2. The enthalpy of formation of ammonia is -46 kJmol-1 and the bond dissociation enthalpies
of nitrogen gas and hydrogen gas are +945 kJmol-1 and +436 kJmol-1 respectively. Calculate
the average bond enthalpy of an N-H bond.
3. June 2003 #3 [10 marks]
(a) Explain the following terms:

(i) Bond energy (2 marks)

(ii) Enthalpy change of combustion, ΔHc (2 marks)

(b) DMSO, dimethylsuphoxide, is an organic liquid having the molecular structure

shown below.

It is an excellent solvent and is known to penetrate the skin very readily. DMSO

has the potential for use as a drug in the treatment of arthritic pain.

Suggest ONE reason for the ability of DMSO to penetrate the skin. (1 mark)

(c) (i) Write an equation for the combustion of DMSO.

(2 marks)

(ii) Use the bond energy data to calculate ΔHc of DMSO.

TABLE 1: BOND ENERGY DATA

Bond Energy/kJ mol-1

C–H 415

C–S 270

S=O 523

O=O 498

O–H 464

C=O 745

(2 marks)

(d) Comment on the suitability of DMSO to use as a fuel.

(1 mark)

Total 10 marks