Reaction Rates and Rate Laws - Complete Interactive Lesson
Part 1: Measuring Reaction Rates
โ๏ธ Measuring Reaction Rates
Part 1 of 7 โ How Fast Does It Go?
Chemical kinetics is the study of how fast reactions occur. While thermodynamics tells us whether a reaction is favorable, kinetics tells us how quickly it reaches products. Some reactions (like explosions) happen in microseconds; others (like rusting) take years.
In this part, we define reaction rate precisely and learn how to measure it.
โ๏ธ Defining Reaction Rate
For a general reaction:
aA+bBโcC+dD
The rate of reaction is defined as the change in concentration of a reactant or product per unit time:
Rate=โa
Key Points
Symbol
Meaning
ฮ[A]
Change in molar concentration of A
ฮt
Change in time
Negative sign for reactants
Reactants are consumed, so ฮ[A]<0; the negative sign makes rate positive
Stoichiometric coefficients
Example
Problem: For 2N2โO5โโ4NO2โ:
Solution:
Rate=โ21โ
If O2โ appears at 0.024 M/s, then NO2โ appears at M/s and disappears at M/s.
Rate Definition Quiz ๐ฏ
โฑ๏ธ Average Rate vs. Instantaneous Rate
Average Rate
The average rate is calculated over a finite time interval:
Averageย rate=โฮtฮ[
Average vs. Instantaneous Rate ๐
โฑ๏ธ Experimental Methods for Measuring Rates
Monitoring Concentration Over Time
Method
What It Measures
Best For
Spectrophotometry
Absorbance (Beer's Law: A=ฮตbc)
Colored solutions
Pressure change
Total gas pressure
Gas-phase reactions
Conductivity
Ion concentration
Reactions producing/consuming ions
Mass loss
Mass of system
Reactions releasing gas
Titration (aliquot method)
Concentration at specific times
Slow reactions
Rate Calculation Drill ๐งฎ
Consider the reaction: 2NO2โโ2NO+O2โ
Time (s)
[NOโ] (M)
Exit Quiz โ Measuring Reaction Rates โ
Part 2: Rate Laws & Orders
๐ก๏ธ Factors Affecting Reaction Rate
Part 2 of 7 โ What Makes Reactions Faster?
Not all reactions proceed at the same speed. Some are explosively fast, while others take geological timescales. In this part, we explore the four major factors that determine how quickly a reaction occurs.
๐ Factor 1: Concentration of Reactants
Higher concentration โ faster rate (usually)
Why?
More particles per unit volume means more frequent collisions. More collisions per second means more chances for a successful (reactive) collision.
Mathematical Connection
The rate law (which we will derive in later parts) often takes the form:
Rate=k[A]m[B
Part 3: Determining Rate Law from Data
๐ Rate Laws
Part 3 of 7 โ The Mathematical Heart of Kinetics
A rate law is a mathematical equation that relates the rate of a reaction to the concentrations of reactants. Rate laws must be determined experimentally โ you cannot simply read them off the balanced equation.
๐ The General Rate Law
For a reaction aA+bBโproducts:
Rate
Part 4: Method of Initial Rates
๐ Method of Initial Rates
Part 4 of 7 โ Systematic Rate Law Determination
The method of initial rates is the gold standard for determining a rate law experimentally. You measure the initial rate of a reaction for several trials, varying concentrations systematically, and use the data to find each reactant's order and the rate constant k.
๐ Step-by-Step Method
Given Data Table Format
Experiment
[A]โ
[B]โ
Initial Rate
1
value
value
value
2
changed
same
value
3
same
changed
value
The Algorithm
Step 1: Assume Rate = k[A]^m[B]^n
Step 2: Pick two experiments where only one concentration changes
Part 5: Factors Affecting Rate
๐ Units of the Rate Constant k
Part 5 of 7 โ How Units Change with Reaction Order
The rate constant k has different units depending on the overall order of the reaction. Understanding why โ and being able to derive or recognize the correct units โ is a key AP Chemistry skill.
๐ Deriving Units of k
Start from the general rate law:
Rate=k[A]m[B
Part 6: Problem-Solving Workshop
๐ง Problem-Solving Workshop
Part 6 of 7 โ Rate Law Problems from Data Tables
This workshop focuses on building fluency with rate law determination from experimental data. You will work through progressively challenging problems that mirror AP Chemistry exam questions.
๐ Problem-Solving Strategy Review
Checklist
โ Write the general rate law: Rate = k[A]^m[B]^n...
โ Identify pairs of experiments differing in only ONE concentration
โ Take ratios to find each order
โ Write the complete rate law with orders
โ Plug in any experiment to solve for k
โ Verify k using a second experiment
โ Check that units of k are consistent with the overall order
Tip for the AP Exam
When the rate ratio is not a clean power, use logarithms:
Part 7: Synthesis & AP Review
๐ Synthesis & AP Review
Part 7 of 7 โ AP-Style Rate Law Determination
This final part brings together all the concepts from Parts 1โ6 with AP exam-level questions. You will work through complete rate law problems including determining orders, calculating k, predicting rates, and interpreting results.
๐ Key Concepts Summary
Rate Expression
For aA+bBโcC+dD:
1
โ
ฮtฮ[A]โ
=
โb1โฮtฮ[B]โ=
+c1โฮtฮ[C]โ=
+d1โฮtฮ[D]โ
Divide by coefficient to get a single, unique rate
+
O2โ
ฮtฮ[N2โO5โ]โ
=
+41โฮtฮ[NO2โ]โ=
+ฮtฮ[O2โ]โ
4ร0.024=0.096
N2โO5โ
2ร0.024=0.048
A
]
โ
=
โt2โโt1โ[A]t2โโโ[A]t1โโโ
Instantaneous Rate
The instantaneous rate is the rate at a specific moment โ the slope of the tangent line to the concentration-vs-time curve:
Instantaneousย rate=โdtd[A]โ
Key Differences
Feature
Average Rate
Instantaneous Rate
Time interval
Finite (ฮt)
Infinitesimally small (dt)
Graphically
Slope of secant line
Slope of tangent line
Accuracy
Approximation
Exact at that instant
As ฮtโ0
Approaches instantaneous rate
โ
Initial Rate
The initial rate is the instantaneous rate at t=0, before significant product buildup. It is especially useful because:
Concentrations are known precisely (the starting concentrations)
Reverse reactions have not yet become significant
It is used in the method of initial rates to determine rate laws
pH measurement
[Hโบ] or [OHโป]
Acid/base reactions
Beer's Law Connection
For colored species, absorbance is directly proportional to concentration:
A=ฮตbc
where ฮต = molar absorptivity, b = path length, c = concentration. By measuring absorbance over time, you can track [coloredย species] over time.
0
0.500
50
0.380
100
0.300
1) What is the average rate of disappearance of NOโ over the first 50 s? (in M/s, 3 significant figures)
2) What is the average rate of the reaction over the first 50 s? (divide by stoichiometric coefficient, 3 significant figures)
3) What is the average rate of appearance of Oโ over the interval 0โ100 s? (in M/s, 3 significant figures)
]n
Increasing [A] or [B] directly increases the rate (when m,n>0).
Example
Burning steel wool in pure Oโ (100%) is dramatically faster than in air (21% Oโ) because the concentration of oxygen molecules is about 5 times higher.
๐ Factor 2: Temperature
Higher temperature โ faster rate
Why?
At higher temperatures:
Molecules move faster โ more frequent collisions
A greater fraction of molecules have enough energy to overcome the activation energy barrier
Rule of Thumb
For many reactions, a 10ยฐC increase roughly doubles the rate. This is an approximation โ the actual factor depends on the activation energy.
Quantitative: The Arrhenius Equation
k=AeโEaโ/(RT)
where:
k = rate constant
A = frequency factor (collision frequency ร orientation factor)
Eaโ = activation energy
R = 8.314 J/(molยทK)
= temperature in Kelvin
We will explore this equation in depth in a later topic.
๐ Factor 3: Surface Area
Greater surface area โ faster rate (for heterogeneous reactions)
Why?
In heterogeneous reactions (where reactants are in different phases), the reaction occurs at the interface between phases. More exposed surface = more contact area = faster reaction.
Examples
Form
Surface Area
Rate
Iron block
Low
Rusts slowly over years
Iron filings
Medium
Rusts in days
Iron nanoparticles
Very high
Can ignite spontaneously
Dust Explosions
Finely powdered combustible materials (flour, coal dust, grain dust) have enormous surface area. If suspended in air, they can ignite and cause devastating explosions. This is why grain elevators have strict safety protocols.
๐ Factor 4: Catalysts
Catalysts speed up reactions without being consumed
How?
A catalyst provides an alternative reaction pathway with a lower activation energy (Eaโ).
Eaโ(catalyzed)<Eaโ(uncatalyzed)
Key Properties of Catalysts
Not consumed โ regenerated at the end of the mechanism
Lower Eaโ โ more molecules have sufficient energy to react
Do NOT changeฮH or ฮG โ thermodynamics is unaffected
Do NOT shift equilibrium โ both forward and reverse rates increase equally
Speed up both directions equally
Types
Type
Description
Example
Homogeneous
Same phase as reactants
Acid catalysis in solution
Heterogeneous
Different phase (usually solid)
Catalytic converter (Pt surface)
Biological
Enzymes
Lactase breaking down lactose
Factors Affecting Rate Quiz ๐ฏ
Match the Factor ๐
Application Problems ๐งฎ
1) A reaction has a rate of 0.020 M/s at 25ยฐC. Using the rough rule that rate doubles with each 10ยฐC increase, estimate the rate at 45ยฐC. (in M/s)
2) If the concentration of a reactant is tripled, and the reaction is second-order in that reactant, by what factor does the rate increase? (whole number)
3) A catalyzed reaction has Eaโ=50 kJ/mol. The uncatalyzed reaction has Eaโ=120 kJ/mol. By how many kJ/mol does the catalyst lower the activation energy?
Round all answers to 3 significant figures.
Exit Quiz โ Factors Affecting Rate โ
=
k[A]m[B]n
Symbol
Meaning
k
Rate constant (temperature-dependent)
[A],[B]
Molar concentrations of reactants
m
Order with respect to A
n
Order with respect to B
m+n
Overall order of the reaction
Critical Points
m and n are NOT necessarily the stoichiometric coefficientsa and b
Orders must be determined from experimental data
Orders can be 0, 1, 2, or even fractional
The rate constant k depends on temperature but NOT on concentration
What Does Order Mean?
Order in A (m)
Effect of Doubling [A]
0
Rate unchanged (ร1)
1
Rate doubles (ร2)
2
Rate quadruples (ร4)
3
Rate increases 8ร
Reaction Order Concepts ๐ฏ
๐ Determining Order from Experimental Data
The Method of Initial Rates
The most common technique: measure the initial rate of reaction for several experiments where you vary one concentration at a time.
Example Data
Experiment
[A] (M)
[B] (M)
Initial Rate (M/s)
1
0.10
0.10
0.015
2
0.20
0.10
0.060
3
0.10
0.20
0.030
Step 1: Find order in A
Compare Exp 1 and 2 ([B] is constant):
Rate1โRate2โโ=k
0.0150.060โ=(0.10
Step 2: Find order in B
Compare Exp 1 and 3 ([A] is constant):
0.0150.030โ=(0.10
Step 3: Write the rate law and find k
Rate=k[A]2[B]
Using Exp 1: 0.015=k(0.10)2(0.10)=k(0.001)
k=0.0010.015โ=15Mโ2
Order Determination Practice ๐งฎ
Given:
Experiment
[X] (M)
[Y] (M)
Initial Rate (M/s)
1
0.10
0.10
0.0020
2
0.30
0.10
0.018
3
0.10
0.30
0.0060
1) What is the order with respect to X? (integer)
2) What is the order with respect to Y? (integer)
3) What is the value of k? (in appropriate units, give the number only โ e.g., if k = 2.0, enter 2.0)
Round all answers to 3 significant figures.
๐ Common Mistakes to Avoid
โ Mistake 1: Using stoichiometric coefficients as orders
For 2NO+O2โโ2NO2โ, the rate law is experimentally found to be:
Rate=k[NO]2[O2โ]
The orders happen to match the coefficients here, but this is coincidence โ it only occurs when the reaction happens in a single elementary step.
โ Mistake 2: Forgetting to hold one variable constant
When comparing experiments to find the order in A, you must choose experiments where [B] is the same. If both change, you cannot isolate the effect of one.
โ Mistake 3: Confusing rate with rate constant
Rate changes as concentrations change during a reaction
Rate constant k is fixed at a given temperature
Rate Law Concepts ๐
Exit Quiz โ Rate Laws โ
Step 3: Take the ratio:
Rate1โRate2โโ=([A]1โ[A]2โโ)m
Step 4: Solve for m using logarithms if needed:
m=ln([A]2โ/[A]1โ)ln(Rate2โ/Rate1โ)โ
Step 5: Repeat for each reactant
Step 6: Substitute back into any experiment to solve for k
Using Logarithms for Non-Integer Orders
If Rate1โRate2โโ=2.83 and [A]1โ[A]2โโ:
m=ln(2)ln(2.83)โ=0.6931.04โ=1.5
So the order is 23โ (fractional order).
๐งช Worked Example 1
For the reaction A+BโC:
Experiment
[A] (M)
[B] (M)
Initial Rate (M/s)
1
0.100
0.100
4.0 ร 10โปโต
2
0.200
0.100
16.0 ร 10โปโต
3
0.100
0.300
4.0 ร 10โปโต
Finding order in A (compare Exp 1 & 2, [B] constant):
4.0ร10โ516.0ร10โ5โ=(
Finding order in B (compare Exp 1 & 3, [A] constant):
4.0ร10โ54.0ร10
Rate law: Rate = k[A]ยฒ (zero-order in B!)
Finding k: Using Exp 1: 4.0ร10โ5=k(0.100)2
Practice Problem 1 ๐งฎ
For the reaction P+QโR:
Experiment
[P] (M)
[Q] (M)
Initial Rate (M/s)
1
0.20
0.10
0.0030
2
0.40
0.10
0.0060
3
0.20
0.20
0.012
1) What is the order with respect to P? (integer)
2) What is the order with respect to Q? (integer)
3) What is the value of the rate constant k? (give the number; e.g., enter 7.5 for 7.5)
Round all answers to 3 significant figures.
๐งช Worked Example 2: Three Reactants
For 2NO(g)+Cl2โ(g)โ2NOCl(g):
Experiment
[NO] (M)
[Clโ] (M)
Initial Rate (M/s)
1
0.10
0.10
0.18
2
0.10
0.20
0.36
3
0.20
0.10
0.72
Order in Clโ (Exp 1 vs 2, [NO] constant):
0.180.36โ=(0.10
Order in NO (Exp 1 vs 3, [Clโ] constant):
0.180.72โ=(0.10
Rate law: Rate = k[NO]ยฒ[Clโ]
Finding k:0.18=k(0.10)2(0.10)=k(0.001)k
Note: The orders (2 and 1) match the stoichiometric coefficients here, but this is coincidental โ it happens because this reaction proceeds via an elementary bimolecular step.
Method of Initial Rates Quiz ๐ฏ
Challenge: Complete Rate Law Determination ๐งฎ
For A+B+CโProducts:
Exp
[A] (M)
[B] (M)
[C] (M)
Rate (M/s)
1
0.10
0.10
0.10
0.0050
2
0.20
0.10
0.10
0.010
3
0.10
0.20
0.10
0.020
4
0.10
0.10
0.30
0.0050
1) What is the overall order of the reaction? (integer)
2) What is the rate constant k? (number only)
3) Predict the rate (in M/s) when [A] = 0.30, [B] = 0.20, [C] = 0.50.
Round all answers to 3 significant figures.
Exit Quiz โ Method of Initial Rates โ
]
n
Rate always has units of M/s (or molยทLโปยนยทsโปยน). Concentration has units of M (mol/L).
Solving for k:
k=[A]m[B]nRateโ
Unitsย ofย k=Mm+nM/sโ=M1โ(m+n)โ sโ1
Summary Table
Overall Order
Units of k
Example
0
Mยทsโปยน (or M/s)
k=M0M/sโ=M/s
1
sโปยน
k=M1M/sโ=s
2
Mโปยนยทsโปยน
k=M2M/sโ=
3
Mโปยฒยทsโปยน
k=M3M/sโ=
The Pattern
Unitsย ofย k=M1โnsโ1
where n = overall order. As order increases by 1, the power of M decreases by 1.
Units of k Quiz ๐ฏ
โ๏ธ Zero-Order Reactions
Rate=k
Rate is constant โ independent of concentration
Units of k: M/s
Half-life: t1/2โ=2k[A]0โโ (depends on initial concentration)
When Do Zero-Order Reactions Occur?
Zero-order kinetics often occur when:
A catalyst or enzyme is saturated โ every active site is occupied
A reaction occurs on a surface that is fully covered
Photochemical reactions where rate depends on light intensity, not concentration
Example
Decomposition of NHโ on a hot tungsten surface: Rate = k. The tungsten surface is saturated with NHโ, so adding more does not increase the rate.
โ๏ธ First-Order and Second-Order Reactions
First-Order (n=1)
Rate=k[A]
Units of k: sโปยน
Half-life: t1/2โ=k0.693โ (independent of concentration!)
Examples: Radioactive decay, many decomposition reactions
Second-Order (n=2)
Rate=k[A]2orRate=k[A][B]
Units of k: Mโปยนsโปยน (for both cases)
Half-life: t1/2โ=k[A] (depends on concentration)
Comparing Half-Lives
Order
t1/2โ
Dependence on [A]0โ
0
Match the Order to Its Properties ๐
Units and k Calculations ๐งฎ
1) A third-order reaction has Rate = k[A][B][C]. What is the power of M in the units of k? (e.g., for Mโปยน, enter โ1)
2) A first-order reaction has k = 0.0250 sโปยน. What is the half-life in seconds? (3 significant figures)
3) A zero-order reaction has k = 0.0040 M/s and [A]โ = 0.80 M. What is the half-life in seconds? (whole number)
Exit Quiz โ Units of k โ
m=log(Concentrationย ratio)log(Rateย ratio)โ
Problem 1: Two-Reactant System ๐งฎ
For A+BโProducts:
Exp
[A] (M)
[B] (M)
Rate (M/s)
1
0.050
0.050
1.25 ร 10โปโด
2
0.100
0.050
5.00 ร 10โปโด
3
0.050
0.100
2.50 ร 10โปโด
1) Order in A? (integer)
2) Order in B? (integer)
3) Value of k? (number only, no units)
Problem 2: Three Experiments, Non-Obvious Ratios ๐งฎ
For X+YโZ:
Exp
[X] (M)
[Y] (M)
Rate (M/s)
1
0.10
0.10
0.0040
2
0.30
0.10
0.036
3
0.30
0.30
0.036
1) Order in X? (integer)
2) Order in Y? (integer)
3) What is the overall order?
Problem 3: AP-Style Question ๐ฏ
For the reaction 2A+BโC+3D:
Exp
[A] (M)
[B] (M)
Rate (M/s)
1
0.10
0.20
0.010
2
0.20
0.20
0.020
3
0.20
0.40
0.080
Problem 4: Finding k and Predicting ๐งฎ
Given Rate = k[M]ยฒ[N] and the following data point: when [M] = 0.25 M and [N] = 0.40 M, the rate is 0.050 M/s.
1) Calculate k (number only, to 3 significant figures)
2) What is the rate when [M] = 0.50 M and [N] = 0.20 M? (in M/s, to 3 significant figures)
3) By what factor does the rate change if [M] is halved and [N] is doubled? (give the number)
Quick Concept Check ๐
Exit Quiz โ Workshop Problems โ
Rate=โa1โฮtฮ[A]โ=+c1โฮtฮ[C]โ
Rate Law
Rate=k[A]m[B]n
Determined experimentally (not from coefficients)
k depends on temperature only
Overall order = m+n
Units of k
Units=M1โ(m+n)sโ1
Key Relationships
If doubling [A] causes rate to...
Order in A
Stay the same
0
Double
1
Quadruple
2
Increase 8ร
3
AP Problem 1 ๐ฏ
The decomposition of N2โO5โ was studied at 45ยฐC:
2N2โO5โ(g)โ4NO2โ(g)+O2โ(g)
Exp
[NโOโ ]โ (M)
Initial Rate (M/s)
1
0.020
4.8 ร 10โปโถ
2
0.040
9.6 ร 10โปโถ
3
0.060
14.4 ร 10โปโถ
AP Problem 2: Complete Analysis ๐งฎ
The reaction A+2BโC was studied:
Exp
[A] (M)
[B] (M)
Rate (M/s)
1
0.10
0.10
3.0 ร 10โปยณ
2
0.20
0.10
1.2 ร 10โปยฒ
3
0.10
0.30
3.0 ร 10โปยณ
1) What is the order with respect to A? (integer)
2) What is the order with respect to B? (integer)
3) What is the value of k? (number only)
Round all answers to 3 significant figures.
AP Problem 3: Conceptual Questions ๐ฏ
Synthesis Review ๐
AP Problem 4: Rate Prediction ๐งฎ
A reaction has rate law Rate = k[A]ยฒ[B] with k = 0.50 Mโปยฒsโปยน.
1) Calculate the rate when [A] = 0.40 M and [B] = 0.60 M. (in M/s, 3 significant figures)
2) If [A] is tripled while [B] is halved, by what factor does the rate change? (to 3 significant figures)
3) What are the units of the rate constant for a reaction that is first-order overall? (enter just the exponent of s: e.g., for sโปยน enter โ1)