CHM1301

Lesson 9
Concentration and reaction rate

Impact of concentration on reaction rate:

● The rate of a given chemical reaction can be expressed as the change of concentration
of a reagent/product over time:
○ Rate of chemical reaction = Δ Concentration of reagent or product
Δ time (s)
● Both the concentration of starting material and products can affect the reaction rate
○ Temperature can also affect reaction rate, but will be discussed in the next
lecture
● The rate of reaction is proportional to the number of collisions
Rate laws: linking rate and concentration
● Rate law: An expression relating the rate of a chemical reaction to the concentration of
reagents
○ Rate = k [A]y[B]x
● The rate constant (k) is the proportionality that links the reaction rate to the concentration
of reagents
● Each concentration has some exponent (y,x), which is called the order of the reaction
with respect to species A & B
● For the given rate law:
○ Rate = k [A]y[B]x
● Order of the reaction: The exponent to which a concentration is raised in the rate law:
○ If y is 1, then the reaction is called first order in A;
○ If x is 2, the reaction is called second order in B;
○ The sum of the individual orders is called the overall order;
● The order of a reaction differs from the stoichiometry of a reaction!
○ Order of a reaction must be determined experimentally
● For example:
○ 2 NO2 (g) + O3 (g) N2O5 (g)+ O2 (g) Experimental Rate = k [NO2]1[O3]1
● The rate cannot be predicted from the overall balanced equation!
● What does the rate law tell us?
■ Rate = k [A]y[B]x
○ Rate law tells us the impact of changing the concentration of reagents on the
overall rate
○ Rate = k [NO2]1[O3]1
■ Double [NO2] = Rate = k [2M]1[1M]1 = 2
■ Double [NO2] & [O3] = Rate = k [2M]1[2M]1 = 4
● A very important statement:
○ The rate law for the rate-determining step (RDS) is the rate law for the overall
chemical reaction

Rate laws and reaction mechanisms

 CHM1301
Lesson 9
Concentration and reaction rate

● Let’s use another example to illustrate the relationship between mechanism and rate
laws:
○ 2 NO 2 (g) 2NO (g)+ O2 (g) Rate = k [NO2]2
● If we write out the elementary steps to this mechanism:
○ Step 1: NO2 (g) NO (g)+ O(g) ← RDS or “slow” step
○ Step 2: O (g) + NO2 (g) NO (g)+ O2 (g) ← “fast” step
“Predicted” vs. “real” rate law
● Every chemical reaction has a different rate law:
○ NO (g) + O3 (g) → NO2 (g)+ O2 (g) vs. O + O3 → 2O2
● The “predicted” rate law vs. the “real” rate law must be compared:
○ Predicted Rate = k [NO2]1[O3]1
● Rate laws must be determined from experimental data
First-Order Reactions
● Let’s use the example of cis-butene to calculate the equation required to undertake
experimental kinetics:

● What is the rate equation to describe the above transformation?

○ Rate = k [cis-2-butene]
● Since we know the first-order rate law:
○ Rate = k [cis-2-butene]
● We know that the change in concentration over time for cis-butene is:
○ Cis-2-butene → trans-2-butene
○ Rate = (-1/a)(Δ [A]/ Δt) ➜ (-1/a)(Δ [cis-2-butene]/ Δt)
● Now we need to rearrange to be able to set these two equations equal to each other:
○ Need to first set equations equal to each other:
■ Generic: (-1/a)(Δ [A]/ Δt) = k [A]
■ Example: (-1/a)(Δ [cis-2-butene]/ Δt) = k [cis-2-butene]
● We can integrate the above relationship determine the change in concentration over
time:
○ (-1/a)(Δ [A]/ Δt) = k [A] ➜ d [A]/ [A] = -ak dt
■ Going to convert Δ to “d”
● If we integrate both sides of the previous equation, we will obtain the following:
[A] t [A] t
○ ∫ d [ A] /[ A ]=∫−akdt ➜ ∫ 1/[ A](d [ A ])=−a ∫ kdt
[A]o ¿ [A]o ¿

● Following with integration, we get the following result:

○ ln [A] – ln[A]o = -akt →Rearrange→ ln [A] = ln[A]o - akt
● We can further rearrange the equation to give:
○ ln [A] = ln[A]o - akt ln [A] = -akt + ln [A]o
● Rate the above equation to exponent “e”:
○ eln [A] = eln [A]o-akt → [A]= [A]oe-akt
 CHM1301
Lesson 9
Concentration and reaction rate

● We can also rearrange the following equation:

○ ln [A] = -akt + ln [A]o
● To give this relationship:
○ ln([𝐴]𝑜 / [𝐴]) = 𝑎𝑘𝑡
● Half-life (t1/2): The time required for the quantity to be reduced by half ([A] =1/2 [A]o)
○ ln([𝐴]𝑜 / [𝐴]) = 𝑎𝑘𝑡 →t1/2→ ln([𝐴]𝑜 0.5/ [𝐴]𝑜) = 𝑎𝑘𝑡1/2
● The equation for t1/2 is:
○ t1/2= ln2 / 𝑎𝑘
Second-Order Reactions
● Similar to the first-order reaction, we need to set the “predicted” rates equal to each
other:
○ 2 NO2 (g) N2O4 (g)
○ (-1/2)(d[A]/ dt) = k [A]2 d [A]/ [A]2 = -2k dt
● Once we move the reagents to one side, we can take the integration
● If we integrate both sides of the previous equation, we will obtain the following:
[A] t [A] t
○ ∫ d [ A]❑2 /[ A]=∫ −2 kdt ➜ ∫ 1/[ A]❑2 (d [ A])=−2∫ kdt
[A]o ¿ [A]o ¿

● Following with integration, we get the following result:

○ 1/[A] – 1/[A]o = 2kt
● If we have the reaction:
○ NO2 (g) + NO2 (g) N2O4 (g)
● The rate law that describes this is:
○ 1/[NO2] – 1/[NO2]o = 2kt
● To calculate the half-life:
○ 1/[A] – 1/[A]o = 2kt
● We know that [A] = ½ [A]o at t = t ½
○ 1/0.5[A]o – 1/[A]o= 2kt ½ → t ½ = 1/2k[A]o
Zeroth-Order Reactions
● Zeroth order reactions are not dependent on concentration of reagents
○ Small fraction of reagent molecules are not in the state they can react;
○ In a reaction of two or more reagents, the concentration of one of them is
massive;
● Consider the equation to the right: A → B
● Rate = k [A]0 → (-1/a)(d[A]/ dt) = k
● If we undertake the integration of the previous equation:
○ (-1/a)(d[A]/ dt) = k
● Simplified, the equation is:
○ d[A] = -ak dt
● Integration results in:
○ [A] = [A]o - akt

How to simplify the behavior of a reaction

● There are two methods that can be used to simplify the behavior of a reaction:
 CHM1301
Lesson 9
Concentration and reaction rate

○ Adjust the conditions so that one reagent is smaller than the others (isolation
method);
○ We measure the rate at the very beginning of the reaction (method of initial rates)
● These two methods are commonly used, but the method of initial rates is the most
common method in chemistry and biology
Summary of Rate Laws: