Kinetics Problem: Decomposition of NH3

1 January 2014

Problem
The decomposition of NH3 is a zero-order reaction whose rate is 2.5x104 mol L1 min1 at 1100 K when [NH3 ] = 0.040 M. 1. Describe the expression of the reaction rate 2. Determine k , the rate constant for the reaction 3. Find the units of k 4. Find the rate of this reaction when [NH3 ] = 0.015 M

Describe the expression of the reaction rate

You are given the rate of reaction in units of mol L1 min1 , which can also be expressed as M1 min1 , or the rate at which the concentration of NH3 varies with time. Further, we know that because NH3 is decomposing, the concentration must decrease with time. Using the language of calculus, we know that the rate of change in a function with respect to time is given by the rst time derivative. Choosing [NH3 ](t) as our function, and knowing that the value of [NH3 ] must decrease with increasing t, we can write an equation for the reaction rate: 1

d[NH3 ] = 2.5x104 mol L1 min1 dt

(1)

Determine k

We have been told that this reaction has zero-order kinetics. The order of reaction kinetics is the sum of the exponents of the concentration terms that appear on the right-hand side of Equation 1. Thus, Equation 1 has zero-order kinetics because there are no concentration terms on the right-hand side. We also know that any rate law can be expressed in a form similar to Equation 1 as given by: d[A] = k [A]a [B ]b [C ]c ... dt (2)

Again, knowing that the decomposition of NH3 is zero-order, we set all of the exponents a, b, c, ... = 0 and obtain: d[NH3 ] =k dt (3)

We then combine Equations 1 and 3 to obtain k = 2.5x104 mol L1 min1 .

Find the units of k

In determining k, we have already found its units: mol L1 min1 , or M min1 . To make sure that we are correct, let us verify that these units make sense for a zero-order reaction. We know from Equation 3 that the rate at which [NH3 ] changes with time depends only on k . Therefore, it follows that k must also have units of concentration per time. Choosing mol L1 as our unit of concentration, and minutes as our unit of time, we see that it is reasonable for k to have units of mol L1 min1 .

Find the reaction rate at a second concentration

From Equation 3, we know that the reaction rate is independent of the concentration of NH3 . Assuming that we have not also varied the temperature at which the reaction is occurring, we conclude that the rate must be the same as when [NH3 ] = 0.040 M, or 2.5x104 mol L1 min1 .

Additional References
An excellent discussion of zero-order reaction kinetics is available on the UC Davis Chemwiki at http://chemwiki.ucdavis.edu/Physical_Chemistry/ Kinetics/Reaction_Rates/Zero-Order_Reactions.