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Concentration changes over time

The order of a reaction leaves a fingerprint: it is the plot that comes out as a straight line. Match the order to the linear plot, and its slope hands you the rate constant.

§1

One order, one straight line.

The integrated rate laws tell how concentration changes with time for each order, and each makes a different plot linear. Zero order: [A] vs time is a straight line. First order: ln[A] vs time is straight. Second order: 1/[A] vs time is straight.

Whichever plot is linear identifies the order, and the slope of that line gives the rate constant k (its sign depending on the form).

Half-life also fingerprints the order. For a first-order reaction the half-life is constant (independent of concentration); for zero and second order it changes with concentration.

UNIT 5 TOPIC 5.3 • CONCENTRATION CHANGES OVER TIME INTEGRATED RATE LAWS The plot that becomes a straight line reveals the reaction order. ZERO ORDER [A] time FIRST ORDER ln[A] time SECOND ORDER 1/[A] time [A]t = [A]0 − kt slope = −k ln[A]t = ln[A]0 − kt slope = −k 1/[A]t = 1/[A]0 + kt slope = +k HALF-LIFE (FIRST ORDER) t1/2 = 0.693 / k Constant — independent of [A]₀. Radioactive decay is a classic first-order example. CED ANCHOR Graphing concentration data three ways and finding which plot is linear identifies the reaction order; the slope of that line gives the rate constant k. AP Chemistry · Unit 5 · Kinetics
Fig. 5.3.1 Integrated rate laws turn order into a straight line. Zero order plots [A] linearly against time; first order plots ln[A]; second order plots 1/[A]. Whichever plot is linear reveals the order, and its slope gives the rate constant. Half-life behavior follows from the order.
§2

Reading the plots.

Match the linear plot to the order, then read k.

  1. Try the three plots. Plot [A], ln[A], and 1/[A] against time.
  2. Find the linear one. Zero order → [A] linear; first order → ln[A] linear; second order → 1/[A] linear.
  3. Read k from the slope. The magnitude of the slope of the linear plot gives the rate constant.
  4. Use half-life as a check. A constant half-life confirms first order; a changing half-life rules it out.
§3

The pieces you'll meet.

Match order, plot, and half-life.

zero
Zero order
[A] vs time is linear; half-life shortens as it proceeds.
first
First order
ln[A] vs time is linear; half-life is constant.
second
Second order
1/[A] vs time is linear; half-life lengthens as it proceeds.
slope
Slope
Gives the rate constant k from the linear plot.
half-life
Half-life
Time to halve the concentration; behavior depends on order.
fingerprint
Linear plot
The plot that is straight reveals the order.
§4

Worked example: identify the order.

Data. For a reaction, a plot of ln[A] versus time is a straight line, but plots of [A] and 1/[A] versus time are curved.

Order. Only ln[A] is linear, which is the fingerprint of a first-order reaction.

Rate constant. The slope of the ln[A] line equals −k, so k is the magnitude of that slope.

Half-life check. A first-order reaction has a constant half-life; measuring it and finding it unchanged as the reaction proceeds confirms first order.

§5

Mistakes that cost real points.

Pitfall · 01

"Half-life behavior has nothing to do with the reaction order."

Half-life is tied to order. A first-order reaction has a constant half-life; a zero-order half-life shortens as the reaction proceeds; a second-order half-life lengthens. The way the half-life behaves is itself a test of order.

Fix. Use half-life behavior as an order fingerprint: constant → first order; changing → zero or second.

Pitfall · 02

"Any straight-line plot's slope gives the rate constant."

Only the correct linear transform for the reaction's order gives k from its slope. If you read the slope off the wrong plot (say, [A] vs time for a first-order reaction), you get a meaningless number.

Fix. First identify which plot is linear (the order), then read k from that plot's slope, not from a curved one.

Pitfall · 03

"A first-order reaction's [A]-vs-time graph is a straight line."

For first order, it is ln[A] vs time that is linear, not [A] vs time (which is curved). Only a zero-order reaction gives a straight [A]-vs-time line. Matching the wrong plot to the order is the classic slip.

Fix. Remember the pairings: zero → [A] linear, first → ln[A] linear, second → 1/[A] linear.

§6

Skill Check.

Ten scenarios. Pick the chips that match your answer, then check. A scenario marks complete the first time every part is right. Progress saves on this device.

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