Chemical KineticsReaction RatesContent level: Core 18 min

Reaction Rates and How They Are Measured

What you'll be able to do: Express a reaction rate correctly from concentration-time data, including the stoichiometric relationships between species.

Introduction

Thermodynamics says whether a reaction can happen. Kinetics asks how fast. Rate is nothing more exotic than a change in concentration divided by the time it took, but the sign conventions and the coefficients trip people up before any real calculation begins.

These are recommended, not required. You can start this lesson at any time.

Learning objectives

  • Calculate an average rate of reaction from concentration-time data
  • Distinguish average, instantaneous and initial rates
  • Relate the rates of different species using the balanced equation
  • Explain qualitatively why rates decrease as a reaction proceeds

Lesson

Rate is a slope

Take the concentration of a species at two times and divide the change by the elapsed time. The result has units of molarity per second. Because a reactant is being used up, its concentration change is negative, so a minus sign is placed in front to make the reported rate positive.

rate = -(1/a) * D[A]/Dt = (1/c) * D[C]/Dt

Why coefficients appear

In 2 NO4 NO + O, nitrogen dioxide appears four times as fast as oxygen. Left alone, each species would report a different number. Dividing each rate by its coefficient collapses all of them onto one unique rate of reaction.

2 NO4 NO + O

Divide by the coefficient, do not multiply. The fastest-changing species has the largest coefficient.

Average versus instantaneous

An average rate is the slope of a straight line joining two points on a concentration-time curve. An instantaneous rate is the slope of the tangent at a single point. Because a typical curve is steepest at the start and flattens later, the average over a long interval always understates the early rate.

If a question gives a table of times and concentrations, it wants an average rate. If it gives a graph and one moment, it wants a tangent.

Initial rate and why it matters

The initial rate is the instantaneous rate the moment mixing finishes. It is the cleanest measurement available because no product has accumulated and no reverse reaction is competing. Every rate law determined by the method of initial rates depends on this.

How rates are measured in practice

Anything that tracks concentration works: colour change followed with a spectrophotometer, gas volume or pressure for a reaction producing gas, mass loss on a balance, pH for reactions producing or consuming hydrogen ions, or conductivity when ion counts change.

Key ideas

Definition
Reaction rate

The change in concentration of a species per unit time, reported as a positive quantity in M/s.

Definition
Average rate

Concentration change divided by the time interval, the slope of a chord on the concentration-time curve.

Definition
Instantaneous rate

The slope of the tangent to the concentration-time curve at a single instant.

Rule
Unique rate of reaction

Divide each species rate by its stoichiometric coefficient and every species gives the same value.

Key concept
Rates slow down

As reactants are consumed, collisions become less frequent, so the curve flattens with time.

Equation
Rate in terms of any species

rate = -(1/a) D[A]/Dt = -(1/b) D[B]/Dt = (1/c) D[C]/Dt

  • a, b, c = stoichiometric coefficients from the balanced equation
  • D[X]/Dt = change in concentration of X divided by elapsed time, in M/s

Worked examples

Worked example 1

In the reaction 2 NO4 NO + O, [NO] falls from 0.100 M to 0.080 M in 50.0 s. Find the average rate of reaction and the rate of formation of NO.

Try it first: Write the concentration change, then decide where the coefficient 2 goes.

    0 of 4 steps revealed.

    Worked example 2

    For N + 3 H2 NH, hydrogen is consumed at 0.030 M/s. At what rate is ammonia formed?

      0 of 2 steps revealed.

      Worked example 3

      A concentration-time curve for a reactant is steep near t = 0 and nearly flat after 200 s. Explain what this shows about the rate.

        0 of 3 steps revealed.

        Common mistakes

        Reporting a negative reaction rate.

        Why it's wrong: The minus sign in the definition exists precisely to make the reported rate positive.

        Check instead: Apply the minus sign to reactant terms, then quote a positive number.

        Multiplying by the coefficient instead of dividing.

        Why it's wrong: That inflates the rate of the species with the largest coefficient instead of normalising it.

        Check instead: Divide each species rate by its own coefficient to obtain the unique rate.

        Treating the average rate over the whole reaction as the initial rate.

        Why it's wrong: The curve is steepest at t = 0, so the whole-run average is always smaller.

        Check instead: Use a tangent at t = 0, or the shortest interval available, for an initial rate.

        Assuming the rate is constant because the equation is balanced.

        Why it's wrong: Stoichiometry fixes ratios, not the time dependence.

        Check instead: Only a zero-order reaction has a constant rate.

        Practice this skill

        No practice questions are available for this topic yet. You can still practice the whole unit.

        What you should now know

        A reaction rate is a change in concentration per unit time, reported as a positive number. Reactant concentrations fall, so their changes carry a minus sign; product concentrations rise, so theirs do not. Dividing each rate by the species coefficient gives one unique rate of reaction that every species agrees on. Average rate uses two points, instantaneous rate is the slope of the tangent at one moment, and the initial rate is the instantaneous rate at t = 0, which is the value used to build rate laws.

        • Rate is a concentration change per unit time, always reported positive
        • Divide each species rate by its coefficient to get the unique rate of reaction
        • Average rate uses a chord, instantaneous rate uses a tangent
        • Initial rate is measured at t = 0 before products interfere
        • Rates fall with time because reactant concentration falls, not because k changes

        Sources and further reading

        • Chemistry 2e, Section 12.1: Chemical Reaction Rates
          Paul Flowers, Klaus Theopold, Richard Langley, William R. Robinson · OpenStax, Rice University · Chapter 12.1
          View source

          Chemistry 2e, OpenStax, Rice University, licensed CC BY 4.0. License