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Unit 2: Chemistry In action

2.1 Energetics

Energetics
After studying this section, you will be able to:
   Enthalpy change ( ΔH ) know that reactions can be endothermic or exothermic understand that enthalpy change (ΔH) is the heat energy change measured under conditions of constant pressure know that standard enthalpy changes refer to standard conditions, i.e. 100 kPa and a stated temperature (e.g. ΔH298) be able to recall the definition of standard enthalpies of combustion (ΔHθc) and formation (ΔHθf) be able to calculate the enthalpy change from the heat change in a reaction using the equation q = mcΔT Know Hess’s Law and be able to use it to perform simple calculations for example calculating enthalpy changes for reactions from enthalpies of combustion or enthalpies of formation. be able to determine mean bond enthalpies from given data be able to use mean bond enthalpies to calculate a value of ΔH for simple reactions

For this topic, review the following definitions: 1. 2. 3. 4. 5. Allotropes Enthalpy Change Endothermic Exothermic Hess’s Law 6. 7. 8. 9. 10. Mean bond enthalpy Specific heat capacity Standard molar enthalpy of combustion, ΔHθc Standard molar enthalpy of formation, ΔHθf Thermochemical cycle

1. Enthalpy Change
Enthalpy, H refers to the amount of heat energy stored in a chemical system. Enthalpy cannot be measured directly but Enthalpy Change, ΔH can be measured by measuring the energy taken from or given to the surroundings following a reaction. Enthalpy Change, ΔH is the heat energy exchange with the environment at constant pressure. Standard Enthalpy Change, ΔHθ refers to enthalpy change under standard conditions, i.e. 1 atmosphere pressure (100 kPa) and 298 K (25oC). ΔHθ also refers to the standard states i.e. physical state of the reactants and products under standard conditions.

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Learning Objective(s)

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Unit 2: Chemistry In action

2.1 Energetics

Chemical reactions are described either as exothermic or endothermic. In exothermic reactions, heat is given out to the surroundings and temperature of the surroundings increases. The products end up with less energy than the starting reactants and the value of ΔH is negative. In endothermic reactions, heat is taken in from the surroundings and temperature of the surroundings decreases. The products end up with more energy than the starting reactants and the value of ΔH is positive. For reversible reactions, if the forward reaction is exothermic, then the backward reaction will be endothermic by the same amount. We use Enthalpy level diagrams (also called reaction profiles or energy level diagrams) to show enthalpy changes

Exothermic

Endothermic

Enthalpy level diagrams above are for an exothermic (left) and an endothermic (right) reaction. Specific enthalpy changes for combustion and for formation reactions are further described under subtopic 3; ‘Using Hess’s Law (Thermochemical Cycle)’ below. In general however, we can refer to the enthalpy change that accompanies any reaction if we know the molar quantities, i.e. if we know the chemical equation for the reaction. Therefore, we refer to the standard molar enthalpy change of a reaction ΔHθr, as the enthalpy change that accompanies a reaction in the molar quantities that are expressed in a chemical equation under standard conditions, all reactants and products being in their standard states. The units are in kj mol-1, kilojoules per mol. For example, ΔHθr for CH4 + 2O2 → CO2 + 2H2O = -890.3 kj, which is the enthalpy change when 1 mole of methane is completely burnt in oxygen to give carbon dioxide and water. But the enthalpy change for 2CH4 + 4O2 → 2CO2 + 4H2O = -890.3 kj X 2 – twice the number of moles as in the first case.

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Unit 2: Chemistry In action

2.1 Energetics

2. Using Calorimetry to measure Enthalpy Changes
We can measure enthalpy changes by measuring the amount of heat energy exchanged with the surroundings. Energy absorbed by or taken from the surroundings causes the temperature of the surroundings (usually water) to change and the energy is determined using the equation:

Q = mcΔT
Where Q is the energy change in joules, m is the mass of the surroundings in g, c is the specific heat capacity of the surroundings in J g-1 oC-1 and ΔT is the temperature change in oC. One way of determining enthalpy change using this method is to determine the enthalpy change when a fuel like ethanol is burnt in oxygen, and the energy given out is used to heat a known mass of water. For example, in an experiment to determine the enthalpy change for the process CH3CH2OH + 3O2 → 2CO2 + 3H2O, the temperature of 200 g of water increased by 8.0 oC when 0.46 g of ethanol was burned. Calculate the enthalpy change in KJ mol-1 (specific heat capacity of water is 4.18 J K-1 g-1. Using Q = mcΔT; heat change = 200 X 4.18 X 8.0 = 6,688 J

BUT molar mass of CH3CH2OH is 46. Therefore, number of moles in 0.46 g of ethanol is 0.01 (0.46÷46) And 0.01 moles releases 6,688J, therefore 1 mole will release = 668,800 J ΔHθc = -668.8 KJ mol-1. (The value is negative because heat is given out, exothermic) The equipment in the diagram is called a simple calorimeter. The value we get for enthalpy change will be less than the actual value because there will be experimental errors arising from the following: I. II. III. IV. some of the heat from the burner escapes to the surrounding air before heating the water Not all of the energy is used to heat the water, some is used to heat the container. Some energy escapes from the water & container before the temperature reading is taken Combustion of the ethanol may not be complete, if oxygen is not abundant Mo Idriss, Quick Revision Notes

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Unit 2: Chemistry In action The value for ΔHθc can be determined more accurately if we use an improvement on the simple calorimeter as shown in the diagram on the right. The insulated container reduces heat loss. We could also shield the burner using a draught screen, to make sure that all the heat from the burner reaches the container. Heat loss can be reduced even further by using what is known as a bomb calorimeter. Here the entire container is enclosed in an airtight enclosure.

2.1 Energetics

3. Using Hess’s Law (Thermochemical Cycle) to indirectly determine Enthalpy
Hess' Law states that "the enthalpy change for a chemical reaction depends only on the initial and final states and is independent of the path followed". In other words whichever route, however direct or indirect, by which the reaction proceeds, the overall enthalpy change for the reaction will be same. It is an application of the principle of conservation of energy. Hess' Law can be used to calculate many enthalpy changes which cannot be measured directly. Many enthalpy changes can be calculated simply by using enthalpies of formation and combustion and applying Hess' Law.

1. Calculations using enthalpies of formation Consider the reaction CH4(g) + Br2(l)  CH3Br(g) + HBr(g) One 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. Since the enthalpy of formation of CH4 is -74.8 kJmol-1 then the enthalpy change when one mole of CH4 is converted into its elements will be +74.8 kJmol-1. Given that the enthalpies of formation of CH3Br and HBr are -37.2 kJmol-1 and -36.4 kJmol-1 respectively, then the enthalpy change for the reaction by this route can be calculated:

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Unit 2: Chemistry In action

2.1 Energetics

CH4(g)

+

Br2(g)

CH3Br(g) -37.2

+

HBr(g)

-74.8

+74.8

-36.4

C(s)

+

2H2(g)

+

Br2(g)

An energetic cycle such as this is known as a Hess' Law cycle. H = -(-74.8) + (-37.2) + (-36.4) = +1.2 kJmol-1

The enthalpy change of any reaction can be calculated if the enthalpies of formation of all the reactants and products are known. The enthalpy of formation of elements in their standard states is always zero. The calculation can be condensed into a simple formula: ∆H = Σ[∆Hf(products)] – Σ[∆Hf(reactants)]

2. Calculations using enthalpies of combustion All organic compounds burn in air to give carbon dioxide and water. Consider the reaction C(s) + 2H2(g)  CH4(g) One 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 (i.e. the reverse of combustion). If the enthalpy of combustion of methane is -890 kJmol-1, then the reverse must be +890 kJ mol1 . The enthalpy of combustion of hydrogen needs to be doubled because there are two moles of hydrogen in the equation. If all the relevant enthalpies of combustion are known, the enthalpy change of the reaction by this route can be deduced.

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Unit 2: Chemistry In action

2.1 Energetics

C(s)

+

2H2(g) (+O2(g)) (-286 x 2) +890 -394 CO2(g)

(+O2(g))

CH4(g) (+2O2(g))

-890

+

2H2O(l)

H = -394 + (2 x -286) - (-890) = -76 kJmol-1

The enthalpy change for a reaction can always be calculated if the enthalpy of combustion of reactants and products are known. The calculation can be condensed into a simple formula: ∆H = Σ[∆Hc(reactants)] – Σ[∆Hc(products)]

4. Bond Enthalpies
During a chemical reaction, the bonds in the reactants are broken. This is an endothermic process; energy is required to do this. After the bonds have been broken, however, the bonds in the products are formed. This is an exothermic process; energy is released when this happens. The 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. It can be calculated from the following equation: H = Energy required to break bonds in reactants - Energy required to break bonds in products. This method can be used to calculate the enthalpy changes for any reaction which does not involve ionic bonds. The breaking and making of ionic bonds involves a more complicated sequence of energetic processes and thus cannot be considered in this way.

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Unit 2: Chemistry In action

2.1 Energetics

a)

Molecules in the gaseous state

In gas phase reactions, the bonds which are broken and formed are covalent bonds. The energy required to separate completely the atoms in one mole of covalent bonds is known as the bond dissociation enthalpy of that bond (Hb). A-B(g)  A(g) + B(g)

Bond C-H O-H C-C C=C C=O H-F H-Cl Cl-Cl Br-Br O=O

H /kJmol-1 +413 +464 +347 +612 +805 +568 +432 +243 +193 +498

These bond enthalpies are mean values; 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-O-H(g)  H-O(g) + H(g); H = +502 kJmol-1 H-O(g)  H(g) + O(g); H = +427 kJmol-1 It is necessary therefore to take an average = ie (502 + 427)/2 = +465 kJmol-1. Thus bond enthalpies calculated from different reactions may vary slightly. They also do not take intermolecular forces into account. Mean bond enthalpies thus only give you approximate values for enthalpy changes.

b)

Solids and liquids

In giant covalent substances, all the covalent bonds have to be broken before free gaseous atoms can be formed.

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Unit 2: Chemistry In action

2.1 Energetics

In either case, the energy required to separate completely the atoms in one mole of the substance is known as the atomisation energy (Hat). M(s)  M(g), or AxBy(s)  xA(g) + yB(g)

Substance C(s)  C(g) Si(s)  Si(g) SiO(s)  Si(g) + 2O(g)

Hat/kJmol-1 +717 +377 +1864

Using mean bond enthalpies to calculate approximate enthalpy changes: The approximate enthalpy change can be calculated by considering the mean bond enthalpies of the bonds broken and bonds formed Eg Consider the combustion of methane: CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)
H H C H H H H H H

+

O O

O O

O

C

O

+

O O

Broken: 4 C-H bonds, 2 O=O bonds: total energy

= (4 x 413) + (2 x 498) = +2648 kJmol-1

Formed: 2 C=O bonds, 4 O-H bonds: total energy So approximate ∆H = 2648 – 3466 = -818 kJmol-1

= (2 x 805) + (4 x 464) = +3466 kJmol-1

This answer is only approximate because it is using mean bond enthalpies, not moleculespecific ones, and because it is ignoring changes in intermolecular forces. The correct value of ∆H for the reaction is -890 kJmol-1. Determining mean bond enthalpies from given data: If 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:

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Unit 2: Chemistry In action

2.1 Energetics

E.g. the enthalpy of formation of methane is known to be -76 kJmol-1. The bond enthalpy of a HH bond is +436 kJmol-1, and the enthalpy of atomization of carbon (C(s)  C(g)) is +713 kJmol-1. Using this information, the mean bond enthalpy of a C-H bond can be calculated. C(s) + 2H2(g)  CH4(g) The bonds broken are the bonds in carbon (C(s)  C(g)) and 2 H-H bonds: Total energy = 713 + 2(436) = 1585 The bonds formed are four C-H bonds: Total energy = 4x (x = mean C-H bond enthalpy) So 1585 – 4x = -76 So 4x = 1585 + 76 = 1661 kJmol-1 So x = 415 kJmol-1 = mean bond enthalpy of C-H Practice Questions

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