In simple terms
A friendly intro before the formal notes — no formulas yet.
Putting a Number on Heat
Reactions release or absorb heat, and enthalpy is our way of bookkeeping that energy. Exothermic reactions hand energy out to the surroundings and warm them up; endothermic reactions pull energy in and cool them down. Measuring the temperature change of the surroundings, or comparing the strengths of the bonds broken and made, lets us pin down exactly how much.
Think of a chemical reaction as a bank account of energy stored in bonds. Breaking bonds is a withdrawal — it costs energy. Making bonds is a deposit — it releases energy. If the deposits are bigger than the withdrawals, the reaction pays out the surplus as heat (exothermic, ΔH negative). If the withdrawals are bigger, the reaction has to draw energy in from its surroundings to balance the books (endothermic, ΔH positive).
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Decide the direction: does the temperature of the surroundings go up (exothermic) or down (endothermic)?
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Measure the heat moved into or out of the surroundings with q = mcΔT.
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Divide by the moles of the reactant that reacted to get an enthalpy change per mole, and attach the correct sign.
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Or estimate it from the data booklet: add up the bond enthalpies of bonds broken, subtract the bond enthalpies of bonds formed.
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Full topic notes
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Exothermic and endothermic reactions
Chemical bonds store energy, and a reaction rearranges those bonds, so almost every reaction transfers energy to or from its surroundings. If the reaction gives out energy — the surroundings get hotter — it is exothermic. Combustion, neutralisation and most oxidation reactions are exothermic; you can feel the heat. If instead the reaction takes energy in — the surroundings get colder — it is endothermic. Dissolving ammonium nitrate, or the thermal decomposition of a carbonate, are endothermic; the flask feels cold. The key is that we judge the direction by what happens to the SURROUNDINGS, because that is what we can actually put a thermometer in.
Exothermic: heat flows OUT of the system into the surroundings. Surroundings warm up. Products have LOWER enthalpy than reactants, so ΔH is NEGATIVE.
Endothermic: heat flows INTO the system from the surroundings. Surroundings cool down. Products have HIGHER enthalpy than reactants, so ΔH is POSITIVE.
The system is the reactants and products; the surroundings are the solvent, the container and the air.
Whatever heat the system loses, the surroundings gain (and vice versa): .
Energy profile diagrams
An energy profile diagram plots enthalpy on the vertical axis against the progress of the reaction on the horizontal axis. The reactants start at one enthalpy level and the products end at another; the difference in height between them is ΔH. Between the two there is a hump — the reaction has to climb over an energy barrier before new bonds can form. The height of that barrier above the reactants is the activation energy, Ea. For an EXOTHERMIC reaction the products sit LOWER than the reactants (the line finishes below where it started, ΔH negative); for an ENDOTHERMIC reaction the products sit HIGHER than the reactants (the line finishes above where it started, ΔH positive).
ΔH is the vertical gap from the reactant level to the product level: products below reactants → exothermic (−); products above → endothermic (+).
Activation energy Ea is the height of the peak measured UP from the reactant level, not from the baseline.
The arrow for ΔH runs from reactants to products; the arrow for Ea runs from reactants up to the top of the hump.
A bigger hump does not change ΔH — activation energy and enthalpy change are independent quantities.
Enthalpy change ΔH: sign conventions and standard conditions
Enthalpy, symbol , is the heat content of a system at constant pressure. We cannot measure the absolute enthalpy of anything, but we can measure the CHANGE that accompanies a reaction, and that is the enthalpy change, . It is defined as the enthalpy of the products minus the enthalpy of the reactants, which is why the sign falls out automatically: if the products hold less energy, ΔH is negative and the reaction is exothermic.
Because the amount of heat a reaction gives out depends on conditions such as temperature and pressure, chemists quote a STANDARD enthalpy change, written , measured under an agreed set of conditions so that values can be compared fairly. ΔH is always quoted per mole of reaction as written in the balanced equation, in kJ mol⁻¹.
Sign convention: exothermic ΔH < 0 (negative); endothermic ΔH > 0 (positive). Never quote an enthalpy change without its sign.
Standard conditions (⊖): pressure 100 kPa, a stated temperature (usually 298 K / 25 °C), each substance in its standard state, and any solutions at a concentration of 1 mol dm⁻³.
Units: kJ mol⁻¹, per mole of reaction as written in the balanced equation.
Doubling the equation doubles ΔH; reversing the equation reverses the sign of ΔH.
The sign is worth marks on its own. A calorimetry answer of '56 kJ mol⁻¹' for an exothermic reaction is incomplete — it must be −56 kJ mol⁻¹. Decide the sign from the physics (did the surroundings warm up or cool down?), not from whatever sign your calculator happens to show.
Measuring ΔH by calorimetry
Calorimetry measures an enthalpy change indirectly, by measuring the temperature change of the surroundings — usually water. A simple calorimeter is an insulated container, such as nested polystyrene cups with a lid, so that the heat released or absorbed by the reaction goes into (or comes from) the water rather than leaking to the room. We measure how much the water's temperature changes and turn that into a heat quantity, q, using the relationship below.
Here is the heat transferred (J), is the mass of the SURROUNDINGS being heated or cooled — the water — in grams, is the specific heat capacity (4.18 J g⁻¹ K⁻¹ for water, from the data booklet), and is the temperature change in K (a change of 1 °C is a change of 1 K, so either unit works). Two steps then turn q into a molar enthalpy change: first, the heat gained by the water equals the heat lost by the reaction but with the opposite sign, so ; second, divide by the number of moles of the reactant that actually reacted and convert from J to kJ.
The single most common calorimetry error is putting the wrong mass into q = mcΔT. m is the mass of WATER (the surroundings), never the mass of the fuel or the solid that dissolved. The mass of the reactant is used separately — to work out the moles when you convert q into ΔH per mole. Keep the two masses in different boxes on your page.
Estimating ΔH from bond enthalpies
A reaction is really the breaking of some bonds and the making of others. Breaking a bond always COSTS energy (it is endothermic), and making a bond always RELEASES energy (it is exothermic). The bond enthalpy is the energy needed to break one mole of a given bond in the gaseous state, and the data booklet lists average values. If the bonds made are stronger, in total, than the bonds broken, the reaction releases a net surplus of energy and is exothermic. This gives a quick way to estimate ΔH without any experiment.
Bonds broken go first (energy in, positive); bonds formed go second (energy out, negative). Broken minus formed.
Count every bond in the balanced equation, remembering coefficients (2 mol HCl means 2 × the H–Cl bond enthalpy).
A negative answer means the bonds formed are stronger overall → exothermic; a positive answer means the bonds broken are stronger overall → endothermic.
It is only an ESTIMATE: tabulated bond enthalpies are averages and strictly apply to gases, so the value differs from a directly measured one.
Common mistakes examiners penalise
Dropping or reversing the sign of ΔH — exothermic must be negative, endothermic positive. Decide the sign from whether the surroundings warmed or cooled, and always write it down.
Using the mass of the fuel or solid in q = mcΔT — m is the mass of the water (the surroundings) that changed temperature, not the mass of the reactant.
Muddling ΔT — ΔT is the CHANGE in temperature (), not a final temperature and not a value converted to kelvin by adding 273 (a change of 7 °C is a change of 7 K).
Forgetting to divide by moles / not converting J to kJ — q from mcΔT is the heat for the amount used, in joules; ΔH is per mole, in kJ mol⁻¹. Divide by n and divide by 1000.
Bond enthalpies the wrong way round — ΔH = bonds BROKEN − bonds FORMED, and you must multiply each bond by its coefficient in the equation.
Measuring activation energy from the baseline — Ea is the height of the peak above the REACTANT level, not above zero.
Confusing q and ΔH — q is the heat measured in the experiment (J, for the amount used); ΔH is the standardised value per mole (kJ mol⁻¹) and carries the opposite sign to q.
Model answer — marked the way our engine marks it
This is the showcase for a calculation topic. In Paper 2 the marks are analytic: each mark is tied to a specific line of working (a method mark, M, or an answer mark, A), and — crucially — the method marks and error-carried-forward (ECF) mean a wrong number early on does not cost you every mark that follows. That is only true if the method is written down. Study how each of the four marks below is earned by a specific line.
Where this leads
Enthalpy is the first step into thermodynamics, the study of what drives reactions. From here, Hess's law lets you combine enthalpy changes you can measure to find ones you cannot; enthalpy cycles use exactly the bond-breaking and bond-making bookkeeping you met above. Later you will add entropy and Gibbs free energy to decide not just how much energy a reaction moves but whether it happens at all. The habit built here — measure the heat, divide by the moles, attach the sign — is the foundation for all of it.
Worked examples
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An energy profile diagram shows the reactants at an enthalpy of 250 kJ, the peak of the curve at 400 kJ, and the products at 100 kJ (all on the same arbitrary scale). (a) State, with a reason, whether the reaction is exothermic or endothermic. (b) Determine ΔH for the reaction. (c) Determine the activation energy, Ea. [4]
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(a) The products (100 kJ) lie BELOW the reactants (250 kJ), so the system loses enthalpy to the surroundings — the reaction is exothermic. [A1]
50.0 cm³ of 2.00 mol dm⁻³ hydrochloric acid is mixed with 50.0 cm³ of 2.00 mol dm⁻³ sodium hydroxide in a polystyrene cup. Both start at 20.0 °C and the temperature rises to a maximum of 33.6 °C. Calculate the enthalpy change of neutralisation in kJ mol⁻¹. (Assume the mixture has the density and specific heat capacity of water: 1.00 g cm⁻³ and 4.18 J g⁻¹ K⁻¹.) [4]
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Step 1 — mass of the surroundings (the water). Total volume = 50.0 + 50.0 = 100.0 cm³, so g. [use mass of solution, NOT of any solid]
Estimate the enthalpy change for the reaction H₂(g) + Cl₂(g) → 2HCl(g) using these average bond enthalpies (kJ mol⁻¹): H–H = 436, Cl–Cl = 242, H–Cl = 431. [3]
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Step 1 — bonds broken (reactants). 1 mol H–H + 1 mol Cl–Cl kJ (energy IN). [M1]
Burning 0.25 g of ethanol raised the temperature of 100 g of water by 12.5 °C. Calculate the enthalpy of combustion of ethanol in kJ mol⁻¹. (c = 4.18 J g⁻¹ K⁻¹) [4]
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Glossary
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Enthalpy (H)
The heat content of a system at constant pressure. Its absolute value cannot be measured; only the CHANGE, ΔH, during a reaction can be measured.
Key takeaways
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Exothermic: heat flows OUT of the system into the surroundings. Surroundings warm up. Products have LOWER enthalpy than reactants, so ΔH is NEGATIVE.
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Endothermic: heat flows INTO the system from the surroundings. Surroundings cool down. Products have HIGHER enthalpy than reactants, so ΔH is POSITIVE.
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The system is the reactants and products; the surroundings are the solvent, the container and the air.
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Whatever heat the system loses, the surroundings gain (and vice versa): .
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Get a Paper 2 calculation marked: calculate an enthalpy change from calorimetry data with full working
Get a Paper 2 calculation marked: calculate an enthalpy change from calorimetry data with full working
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