12ChF322 - Energy

Enthalpy Changes
Candidates should be able to: (a) explain that some chemical reactions are accompanied by enthalpy changes that can be exothermic (H, negative) or endothermic (H, positive); (b) describe the importance of oxidation as an exothermic process in the combustion of fuels and the oxidation of carbohydrates such as glucose in respiration; (c) describe that endothermic processes require an input of heat energy, eg the thermal decomposition of calcium carbonate; (d) construct a simple enthalpy profile diagram for a reaction to show the difference in the enthalpy of the reactants compared with that of the products; (e) explain qualitatively, using enthalpy profile diagrams, the term activation energy; (f) define and use the terms: (i) standard conditions, (ii) enthalpy change of reaction, (iii) enthalpy change of formation, (iv) enthalpy change of combustion; (g) calculate enthalpy changes from appropriate experimental results directly, including use of the relationship: energy change = mcT; (h) explain exothermic and endothermic reactions in terms of enthalpy changes associated with the breaking and making of chemical bonds; (i) define and use the term average bond enthalpy (H positive; bond breaking of one mole of bonds); (j) calculate an enthalpy change of reaction from average bond enthalpies; (k) use Hess law to construct enthalpy cycles and carry out calculations to determine: (i) an enthalpy change of reaction from enthalpy changes of combustion, (ii) an enthalpy change of reaction from enthalpy changes of formation, (iii) an enthalpy change of reaction from an unfamiliar enthalpy cycle.

Enthalpy is chemical energy. We are interested in enthalpy changes changes in chemical energy which accompany reactions. We define the enthalpy change of reaction as the enthalpy change when the number of moles of reactants, as specified in a balanced equation, react together. Consider Mg + O2 MgO - the magnesium burns with a white flame, lots of heat is given out.
Mg + O2
Energy given out

enthalpy

MgO

Lower enthalpy: more stable bonds get stronger H is -ve

progress of reaction

The products are lower in enthalpy than the reactants which is what we mean by the reaction is exothermic. We would often say that the products are (thermodynamically) more stable than the reactants an idea associated with the bonds in MgO being stronger than those in Mg and O2. An exothermic reaction is a reaction which gives out heat energy to its surroundings, because the reactants react with a decrease of internal energy (enthalpy). Oxidation reactions are exothermic e.g. the combustion (burning) of fuels to produce useful energy. Page 1

12ChF322 - Energy Another exothermic reaction is respiration oxidation of carbohydrates such as glucose to produce energy for the body. Endothermic reactions require an input of heat energy. Most endothermic reactions are therefore carried out at a high temperature, e.g. the decomposition of carbonates such as calcium carbonate. This is done industrially in a lime kiln at 1000C. The high temperature gives the energy needed to break bonds (i.e. to exceed the activation energy for the reaction). It also speeds up the reaction. For these reactions the change in chemical energy is positive, H +ve. Bond breaking Energy is needed to break bonds. This energy is called the bond enthalpy. Bond enthalpies are positive values because energy has to be supplied to break the bonds, so bond breaking is an endothermic process. e.g. H2(g) H(g) + H(g) H = +436 kJ mol-1

Definition: The bond enthalpy is the energy required to break 1 mole of a specific bond in a substance, in the gaseous state. (i.e. free from the influences of intermolecular forces from other substances nearby). The bond enthalpies given in tables are average bond enthalpies. They are averages because they are determined using the same bond but from many different molecules. They are hard to measure directly usually they are determined using enthalpy changes on combustion of these molecules. Note: Bond enthalpies are appropriate to use for bonds in gaseous compounds only. We can add up the average bond enthalpies for all the bonds in a substance to determine the energy required to break it down into its component atoms. e.g. H2CO (methanal) contains 2 x C-H and 1 x C=O bonds The total bond enthalpy is (2 x + 413) + (1 x +750) = 1576 kJmol-1

Bond making Energy is given out when bonds are formed. The amount given out is equal and opposite to the bond enthalpy (i.e. the same value, but negative). Bond formation is therefore an exothermic process. e.g. When CO2 is formed from its component atoms, 2 x C=O bonds are made, therefore the energy given out is 2 x -750 = -1500 kJ mol-1 Reactions are described as exothermic or endothermic overall depending on whether energy is given out or taken in overall in other words depending on the overall enthalpy change. First of all, bonds in the reactants need to be broken an endothermic step with a positive enthalpy change then new bonds need to be made an exothermic step with a negative enthalpy change. If the energy taken in to break the bonds is greater than the energy given out when the products form, then the reaction is endothermic. If the energy Page 2

12ChF322 - Energy given out is greater than the energy needed to break the bonds in the reactants, then the reaction is exothermic. For example: Bonds broken: CH4 + 2O2 CO2 + 2H2O 4 x C-H = 4 x +413 Bonds made: 2 x C=O = 2 x -750 2 x O=O = 2 x+498 4 x H-O = 4 x -464 Total = +2648 kJ mol-1 Total = -3356 kJ mol-1 H = sum of bonds broken + sum of bonds made H = +2648 3356 = -708 kJmol-1 so the reaction is exothermic (H ve)

To get a reaction to happen, we have to break the necessary bonds in the reactants. This bond-breaking step requires an amount of energy called the Activation Energy (EA). Reactions with a low EA are likely to go faster. In an exothermic reaction, the heat given out continues to provide the EA as the reaction continues. Endothermic reactions need to be heated (or an alternative energy supplied e.g. light) to keep providing the EA). We show enthalpy changes using an enthalpy profile diagram;, enthalpy on the y-axis against progress of the reaction along the x-axis (a sort of time axis).
C + 4 H + 4O enthalpy (kJ mol-1) EA + 2648 kJmol-1 CH4 + 2O2 reactants - 708 kJmol-1 CO2 + 2H2O products progress of reaction - 3356 kJmol-1

It is easy to see from an enthalpy profile diagram whether a reaction is exothermic or endthothermic, and we can also show the Activation Energy (EA) the energy required to break the necessary bonds in the reactants (which is the same as minimum energy the reactant need to collide with in order for a reaction to be successful.

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12ChF322 - Energy

Enthalpy

EA reactants

products H

Enthalpy diagram for an endothermic reaction (H +ve)

progress of reaction

EA Enthalpy reactants H products progress of reaction Enthalpy diagram for an exothermic reaction (H -ve)

EA fwd Enthalpy A H fwd H reverse B

EA reverse

Enthalpy diagram for an reversible reaction A B

progress of reaction

Standard enthalpy changes Standard conditions, denoted with a symbol, are needed in order to compare enthalpy changes fairly. For enthalpy changes we use 298K (25C) and 1 atmosphere (101kPa). It is also necessary that every substance must be in its normal state under these conditions, which we show by using the correct state symbols. In particular we define Standard Enthalpy Changes for combustion reactions, and for the formation of compounds from their elements. The standard enthalpy change of formation (Hf) is the enthalpy change when one mole of a substance is formed from its elements under standard conditions of temperature and pressure (298K and 101kPa).

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12ChF322 - Energy We may be asked to write an equation to illustrate this, e.g. the standard enthalpy change of formation of calcium oxide would be represented as: Ca(s) + O2(g) CaO(s)

because calcium is a solid metal at 25C and oxygen is a gas at 25C and 101kPa, and the calcium oxide formed is a solid under these conditions. The equation is balanced to show just 1 mole of CaO being made, using fractions on the left hand side as necessary. Check your understanding: i) Write an equation to show the standard enthalpy change of formation of ethanol, C2H5OH The standard enthalpy change of combustion, Hc, is the enthalpy change when one mole of a substance is completely burned (i.e. in an excess of oxygen) under standard conditions of temperature (298K) and pressure (101kPa). We may be asked to write an equation to illustrate this, e.g. the standard enthalpy change of combustion of ethane should be shown as: C2H6(g) + 3 O2(g) 2CO2(g) + 3H2O(l) because ethane, oxygen and carbon dioxide are gases at 25C and 101kPa, and water is a liquid, and because the equation has been balanced to show exactly one mole of ethane being burnt (despite needing to use a fractional number of moles of oxygen). Check your understanding: ii) Write an equation to show the standard enthalpy change of combustion of ethanol. The standard enthalpy change of neutralisation is the enthalpy change when 1 mole of an acid (or base) is neutralised by a base (or acid) under standard conditions of temperature and pressure. We use standard enthalpies for making fair test comparisons an example might be comparing different fuels to determine how much energy each produces per mole of CO2 released into the atmosphere: e.g. CH4 + 2O2 CO2 + 2 H2O C8H18 + 12 O2 8CO2 + 9H2O Hc = -890 kJ mol-1 Hc = -5472 kJ mol-1

Therefore octane produces 5472 8 = 684 kJ per mole of CO2 produced. Methane produces 890 kJ of energy per mole of CO2 produced, showing that methane is a more environmentally friendly fuel than octane.

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12ChF322 - Energy Standard enthalpy changes of other reactions: The standard enthalpy change of a reaction Hr can be worked out using the average bond enthalpies for bonds broken and made SO LONG AS the reactants and products are gases (as shown in the equation) under standard conditions, because the average bond enthalpies are determined for bonds in gaseous substances only: e.g. 2 SCl2(g) S2Cl2(g) + Cl2(g) Average bond enthalpies (kJ mol-1) S-Cl 255 S-S 266 Cl-Cl 242 + 1 x Cl-Cl bond made + 1 x -242

Hr = 2 x S-Cl bonds broken + 1 x S-S bond made = 2 x 255 + 1 x -266

= + 2 kJ mol-1 (so the reaction is slightly endothermic) Hesss Law In a reversible reaction, the sign of H for the forward and the backward reaction is equal and opposite. This is a consequence of the law of conservation of energy. Hess's law is based on this idea and states that: The total enthalpy change for a reaction is the same no matter which route the reaction takes, provided the initial and final conditions are the same.

B enthalpy A HAC C progress of reaction practice, Hess's Law means

= HAB + HBC

HAB

HBC

In that

HAC

We can use this to help calculate the enthalpy change during a reaction if we know other enthalpy changes and can form a cycle. We would want to do this for any reaction where we couldn't measure the enthalpy change directly e.g. because the reaction doesn't work at all, or only happens inside a complex system such as photosynthesis.

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12ChF322 - Energy Example: C + O2 CO H = -110 kJmol-1 CO + O2 CO2 H = -283 kJmol-1 C + O2 CO2 H = -393 kJmol-1 We can draw a Hess Cycle for this: C + O2 H = -110 kJmol-1 CO + O2 We can see that the cycle works because -110 + -283 = -393 H = -393 kJmol-1 CO2 H = -283 kJmol-1

Reversible reactions We can also see why the enthalpy change in a reversible reaction is equal and opposite. Consider A B + C A H2 H1 = - H2 because the energy change is the same regardless of the path. H1 B + C

Using bond enthalpies in a Hess Cycle We can use the format of a Hess Cycle to work out an enthalpy change for a reaction rather than the tabular format used before if we prefer. The calculation is exactly the same. for example: CH4 + 2 O2 CO2 + 2 H2O Average bond enthalpies (kJmol-1) C-H 413 O=O 498 C=O 750 H-O 464
CO2 + 2 H2O bonds broken: 2 x C=O 2 x 750 4 x H-O 4 x 464 + 3356

CH4 + 2 O2 bonds broken: 4 x C-H 4 x 413 2 x O=O 2 x 498 + 2648

Hc = ?

C+ 4H+ 4O

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12ChF322 - Energy Using the Hess Cycle, Hc = +2648 + (-3356) = -708kJmol-1 i.e. its exothermic

The book value for Hc = -890 kJmol-1. Why the discrepancy ? Because Hc calculated with bond enthalpies assumes all reactants and products are gases (because that's how bond enthalpies are stated). Standard conditions requires the states to be correct at room temp and pressure, and under these conditions water is a liquid, not a gas. Using enthalpies of combustion in Hess Cycles Enthalpies of combustion are comparatively easy to measure experimentally, and so are used to calculate the enthalpy changes for other reactions which would not be so easy to do directly. We can work out any kind of enthalpy change (reaction, combustion, formation) this way doesn't matter. What is key is what kind of data we are given in the question. In this type of question we'll be given Hc values to work with. The layout is always the same: REACTANTS Hr = ? PRODUCTS

products of complete combustion Example: Carbon and hydrogen don't react to form methane when directly mixed, but if they did react, would the reaction be exothermic or endothermic ? (What we are working out here is actually the enthalpy change of formation of methane) C(s) + 2 H2(g) CH4(g) H r = ?

We can use the standard enthalpies of combustion for carbon and for hydrogen, and for methane. All will burn readily and the energy released can be measured. C(s) + O2(g) H2(g) + O2(g) CH4(g) + 2 O2(g) H2O(l) CO2(g)

H c = -394 kJmol-1 H c = -286 kJmol-1

CO2(g) + 2 H2O(l)

H c = -890 kJmol-1

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12ChF322 - Energy Now we can draw the Hess Cycle: C(s) + 2 H2(g) + 2 O2(g) 2 x -286 Hr = ? CH4(g) + 2 O2(g)

-394

-890

CO2(g) + 2 H2O(l) And calculate H r = -394 + (2 x -286) + 890 = -76 kJmol-1 So the reaction would be exothermic if it happened. Checking a Hess cycle The 'MASK' check M moles correctly multiplied up for each arrow, according to balanced equation A arrows in correct direction depending on type of Hess cycle S signs correctly transferred from arrows into the calculation K knowledge (does the answer fit with your experience ?) Check your understanding: iii) Calculate the enthalpy change for the same reaction, C(s) + 2 H2(g) CH4(g), using the average bond enthalpies given: H-H + 436kJmol-1 C-H +413kJmol-1 iv) Suggest why the value obtained this way is so different from that you calculated using enthalpies of combustion. v) Calculate H r for the cracking of decane to give octane and ethene using the standard enthalpy changes of combustions given in an appropriate Hess Cycle: decane, H c = -6777.9 kJmol-1 octane, H c = -5470.2 kJmol-1 ethene H c = -1410.8 kJmol-1 In general, if we prefer to use maths rather than the diagrammatic approach, we can use the equation below when we are given enthalpies of combustion, so long as we remember to multiply the H c values by the appropriate number of moles : H r = H c reactants - H c products

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12ChF322 - Energy Using enthalpies of formation in Hess Cycles Enthalpies of formation are also available in the data books, and are also very useful for calculating enthalpy changes for "inaccessible" reactions. We can work out any kind of enthalpy change (reaction, combustion, formation) this way. What is key is what kind of data we are given in the question. For these we'll be given Hf values to work with. The layout is always the same: REACTANTS Note the different direction of the arrows ! Hr = ? PRODUCTS

elements from which these are made We can write a general mathematical formula in the same way as before if we prefer: H r = - H f reactants + H f products For example, we can consider the cracking of decane as before and prove that we can get the same answer regardless of what type of enthalpy changes we use in the Hess cycle. We'll need the enthalpies of formation of decane, octane and ethene: decane octane ethene decane C10H22 Hr = ? -250.0 H f H f H f

= -300.8 kJmol-1 = -250.0 kJmol-1 = +52.2 kJmol-1 octane + ethene C8H18 + C2H4

-300.8

+52.2

10 C + 11 H2

So H r = +300.8 250.0 + 52.2 = +103.1 kJmol-1 (which should be the same as you got with the previous "Check your Understanding" question !)

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12ChF322 - Energy Check your understanding: vi) A reaction to manufacture hydrogen for use in the Haber process is carried out at high temperature, using natural gas and steam: CH4(g) + H2O(g) CO(g) + 3 H2(g) Use the given enthalpies of formation to work out the enthalpy change for this reaction. Hf values (kJmol-1) CH4(g) -75 H2O(g) -242 CO(g) -110 Equation for the enthalpy change of formation C + 2 H2 CH4 H2 + O2 H2O C + O2 CO

Finding missing data We may be given some Hc or Hf values and the Hr for a reaction and be required to work out a missing enthalpy change. The Hess Cycle is used in exactly the same way. Example: The standard enthalpy change of combustion of methanol, H c = -726.0 kJmol-1. Construct a Hess Cycle to calculate the standard enthalpy change of formation of methanol, H f, given the enthalpy changes of formation of carbon dioxide and water. H f CO2 = -393.5 kJmol-1 H f H2O = -285.8 kJmol-1 CH3OH + 1 O2 Hf = ? Hc = -726.0 -393.5 2 x -285.8 C + 2H2 + 2O2 So H f for methanol = -393.5 + (2 x -285.8) + 726.0 = -239.1 kJ mol-1 Calorimetry When the temperature of a substance is changed, the amount of energy needed to cause this can be calculated: Heat energy required is given by the equation: Q = m c T

C(s) + O2(g) CO2(g) H2(g) + O2(g) H2O(l) CO2 + 2 H2O

Where Q = energy required (J) m = mass of stuff getting heated (g) c = specific heat capacity (Jg-1K-1) usually 4.18 or 4.2, given in question T = change in temperature (K) = final temp initial temp remember to show the sign too !

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12ChF322 - Energy The source of this heat may be a chemical reaction, in which case the heat energy was produced by a change in chemical energy an enthalpy change. The enthalpy change is given by: H = -Q / (moles of reactant x 1000) Where H is in kJmol-1 (Note: the factor of 1000 is to convert J to kJ) moles = moles of whichever reactant in NOT in excess We must also check that the sign of H is correct ! If the temperature increased, the reaction was exothermic and H must have a sign. If the temperature decreased, the reaction was endothermic and H has a + sign. SHOW + SIGNS ! For liquids/solutions which get heated, we may know the volume rather than the mass. We need to convert volume to mass. This is done using density: mass (g) = volume (cm3) x density (g cm- 3) The density of pure water is 1.00 g cm-1, so essentially the mass of the liquid will be the same as the volume. You will be given the actual density to use if a calculation is needed. e.g. 50cm3 each of two solutions A and B with density 1.00 g cm-1 at 18C were reacted together. The resulting temperature rose to 31.9C. Calculate the heat energy produced in this reaction: Q = mass x 4.18 x (31.9 - 18) mass = (50 + 50) x 1.00 so mass = 100g Q = 100 x 4.18 x 13.9 = +5810 Joules During the reaction 0.1 moles of B reacted with an excess of A. Calculate the enthalpy change of the reaction: H = -Q / (moles x 1000) = -5810 / (0.1 x 1000) = -5.8 kJ mol-1 Check: The reaction was exothermic temperature INCREASED so the sign of H has to be negative A common mistake is to use the mass of the reactants rather than the mass of the substance whose temperature is being measured these are not always the same ! Consider the following three examples, and for each decide what value of mass to use in order to calculate Q and what number of moles to use to calculate H.

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12ChF322 - Energy

Mass to use = 150g since 150cm3 of solution after mixing. Moles to use = 0.1 x 50/1000 = 0.005 moles (based on NaHCO3 since HCl was in excess)

Mass to use = 100g since we used 100cm3 of solution with density of 1.00 g cm-3 (ignore the mass of the solid, since its specific heat capacity will be very low) Moles to use depends on which is in excess. Moles NaOH = 1 / (23 + 16 + 1) = 0.025 moles Moles HCl = 0.5 x (100/1000) = 0.050 moles (excess, so we use moles of NaOH)

Mass is 200g since 200cm3 of water gets heated Moles = mass/RFM = 0.46/46 = 0.01 moles of ethanol burnt. Page 13

12ChF322 - Energy Check your understanding: use c = 4.2 Jg-1K-1 vii) Calculate Q and hence H for example 1 if the temperature on reaction dropped from 20.0C to 2.5C viii) Calculate Q and hence H for example 2 if the temperature on reaction increased from 15.0C to 21.2C ix) Calculate the temperature change expected in example 3 given that Hc of ethanol is -1367 kJ mol-1

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12ChF322 - Energy

Answers to Check your Understanding questions:

i) Write an equation to show the standard enthalpy change of formation of ethanol, C2H5OH C(s) + 3 H2(g) + O2(g) C2H5OH(l) ii) Write an equation to show the standard enthalpy change of combustion of ethanol C2H5OH(l) + 3 O2(g) 2 CO2(g) + 3 H2O(l) iii) Calculate the enthalpy change for the reaction, C(s) + 2 H2(g) CH4(g) using the average bond enthalpies given: H-H + 436kJmol-1 C-H +413kJmol-1 Bonds broken: Bonds made: H = 872 1652 2 x H-H = 2 x 436 = 872 kJ mol-1 4 x C-H = 4 x 413 = 1652 kJ mol-1 = -780 kJ mol-1

iv) Suggest why the value obtained this way is so different from that calculated using enthalpies of combustion (which was -76 kJ mol-1): The difference can be seen if we look at the equations for the two reactions: C(s) + 2 H2(g) CH4(g) Hf = -76 kJmol-1 C(g) + 2 H2(g) CH4(g) Hr = -780 kJmol-1 The C(s) C(g) step requires a lot of energy to vaporise the carbon (i.e. to break all the C-C bonds in the solid carbon lattice), so the energy released when the carbon has to be vapourised as well is much lower. v) Calculate H r for the cracking of decane to give octane and ethene using the standard enthalpy changes of combustions given in an appropriate Hess Cycle: decane, H c = -6777.9 kJmol-1 octane, H c = -5470.2 kJmol-1 ethene H c = -1410.8 kJmol-1 decane C10H22 + 15 O2 Hr = ? -5470.2 octane + ethene C8H18 + C2H4 + 15 O2

-6777.9

-1410.8

10 CO2 + 11 H2O

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12ChF322 - Energy So H r = -6777.9 + 5470.2 + 1410.8 = +103.1 kJmol-1 (endothermic, as expected for a thermal decomposition) vi) A reaction to manufacture hydrogen for use in the Haber process is carried out at high temperature, using natural gas and steam: CH4(g) + H2O(g) CO(g) + 3 H2(g) Use the given enthalpies of formation to work out the enthalpy change for this reaction. Hf values (kJmol-1) CH4(g) -75 H2O(g) -242 CO(g) -110 CH4 + H2O -242 Equation for the enthalpy change of formation C + 2 H2 CH4 H2 + O2 H2O C + O2 CO Hr = ? CO + 3 H2

-75

-110

no arrow its an element so it takes no energy to form it from its elements !

C + 3H2 + O2

Hr = +75 + 242 110 = +207kJ mol-1 which is endothermic (hence the need for high temp). vii) Calculate Q and hence H for example 1 if the temperature on reaction dropped from 20C to 2.5C Q = mcT = 150 x 4.2 x (2.5 - 20.0) = 150 x 4.2 x -17.5 = -1102.5 Joules H = +1102.5 / (0.005 x 1000) = + 220.5 kJ mol-1 Sign of H is positive since temperature decreased in reaction viii) Calculate Q and hence H for example 2 if the temperature on reaction increased from 15C to 21.2C Q = mcT = 100 x 4.2 x (21.2 15.0) = 100 x 4.2 x 6.2 = +2604 Joules H = -2604 / (0.025 x 1000) = -104.16 kJ mol-1 Sign of H is negative since temperature increased in reaction ix) Calculate the temperature change expected in example 3 given that Hc of ethanol is -1367 kJ mol-1 Using H = -Q / (moles x 1000) -1367 = -Q / (0.01 x 1000) So Q = 13670 Joules Using Q = mcT So T = +16.3C 13670 = 200 x 4.2 x T

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