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Chemistry

Reaction Kinetics

5,152 words, 10 sections. The first two are free.

The opening sections

Definitions first, then the reasoning. Each section is short enough to read in one sitting.

Chemical kinetics is the branch of chemistry that asks not whether a reaction can happen, but how fast it goes and by what route. The chapter carries 201 distinct questions across 83 official papers between 2003 and 2026, with a mean item difficulty of 1.68. Chemistry is worth 45 of the 180 marks, and within this chapter, reaction rates and rate laws account for 144 questions, reaction mechanisms and catalysis for 29, and activation energy and the rate constant for 28. A student who has this chapter under control can turn a table of concentrations or initial rates into a rate law, read the order of a reaction off the units of its rate constant, explain why a rise of ten kelvin roughly doubles a rate, and say precisely how a catalyst, a powdered solid or a warm flask changes a reaction without ever moving its equilibrium.

A chemical reaction does not finish in an instant. The rate of reaction is the change in concentration of a reactant or a product per unit time, and for a species XX it is written as rate=Δ[X]Δt\text{rate} = \frac{\Delta [X]}{\Delta t}. Because concentration is measured in mol dm−3\text{mol dm}^{-3} and time usually in seconds, the rate carries the units mol dm−3 s−1\text{mol dm}^{-3}\text{ s}^{-1}; in a gas-phase reaction the concentration term is often replaced by a pressure. For the simple change A→BA \rightarrow B, the rate can be followed either as the disappearance of AA, −Δ[A]Δt-\frac{\Delta [A]}{\Delta t}, where the minus sign keeps the rate positive, or as the appearance of BB, +Δ[B]Δt+\frac{\Delta [B]}{\Delta t}.

The rate is not constant during a reaction. Plot concentration against time and the curve is steepest at the start, where the reactants are most concentrated, then flattens as they are used up. The average rate over a chosen interval is the change in concentration divided by the interval, while the instantaneous rate is the slope of the tangent drawn at that instant. Because the slope is greatest near the beginning, the instantaneous rate is highest at the start and falls as the reaction proceeds. When the equation has coefficients the rate is shared among the species: for 2A+2B→3C2A + 2B \rightarrow 3C the one rate of reaction is −12Δ[A]Δt=−12Δ[B]Δt=+13Δ[C]Δt-\frac{1}{2}\frac{\Delta [A]}{\Delta t} = -\frac{1}{2}\frac{\Delta [B]}{\Delta t} = +\frac{1}{3}\frac{\Delta [C]}{\Delta t}.

Chemical kinetics is the name for the whole study, the rate of a reaction, its mechanism, and the factors that change its speed. Where a reaction makes or removes ions, the rate can be followed by watching the change in electrical conductivity, because the ion concentration governs how well the solution conducts. This is the standard way to follow a reaction between ions, as opposed to watching a colour fade or reading a pressure gauge.

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