The Steady-State Approximation

(Zumdahl Section 15.7)

In some reactions there is no single step in the mechanism that is much slower than the others. This complicates the methods described in the previous section. In such cases, we resort to a Steady-State Approximation, in which we assume that the concentrations of reactive intermediates remain nearly constant through most of the reaction.

Steady-State Example: 2NO(g) + H2(g) --> N2O(g) + H2O(g)

Proposed Mechanism: k1 2NO k-1 N2O2 + H2 k2 N2O2 N2O + H2O

The double arrows in the first step indicate that both the forward and reverse of this step are important on the time scale of the overall reaction. Let's make the approximation: [N2O2] is constant

Example (cont)
If [N2O2] is constant, then d[N2O2]/dt = 0 k1 2NO N2O2 k-1 N2O2 + H2
Rate of production of N2O2 d[N2O2]/dt = k1[NO]2

k2

N2O + H2O
Rate of consumption of N2O2 -d[N2O2]/dt = k-1[N2O2] + k2[N2O2][H2]

Steady-State Condition:
k1[NO]2 = k-1[N2O2] + k2[N2O2][H2]

Example (cont):
We now use this information to determine the rate law for the overall reaction:

2NO(g) + H2(g) --> N2O(g) + H2O(g)

Rate of reaction = -d[H2]/dt = k2[H2][N2O2]
(from 2nd step of mechanism)

Solving the steady-state equation for [N2O2] and substituting into this rate equation gives: Rate = -d[H2]/dt = k2[H2] k 1 -1 + k2[H2]
k [NO]2

Example (cont): 2NO(g) + H2(g) --> N2O(g) + H2O(g)

k1[NO]2 Rate = -d[H2]/dt = k2[H2] k + k [H ] -1 2 2

To test this mechanism, we can test the rate law by changing the concentrations of H2 and NO
For large [H2], k2[H2] >> k-1 and Rate k1[NO]2

For large [NO], k2[H2] << k-1 and Rate k2[H2][NO]2

The limiting rate laws obtained from the steady-state approximation provide predictions that we can test

A Model for Chemical Kinetics

(Zumdahl Section 15.8)

Concentrations of reactants affect rates So does temperature So do catalysts Obviously, a rate constant is not really a universal constant, but is constant only for a fixed set of experimental conditions.

How do we explain the dependence of reaction rates on temperatures and catalysts? i.e. Where do Rate Constants come from?

Collision Theory of Reactions

Consider a gas phase reaction: 2A(g)
This reaction requires collision of 2 reactants. We can calculate the collision frequency from the ideal gas law. We can also measure the reaction rate experimentally. For such reactions, the reaction rate is typically several orders of magnitude slower than that predicted from the collisional frequency alone. products

We can conclude that not every collision of reactants results in a successful reaction.

One obvious candidate is molecular orientation: only the correct orientation of reactants will lead to successful product formation

What factors might keep the two reactants from reacting once they have collided?

Figure15.11

This could account for perhaps 1 order of magnitude, but not for the several orders of magnitude reduction in rates observed experimentally. The answer must be more complex.

A clue comes from the strong temperature dependence of many rate constants: Note that this temperature dependence is not linear In 1877, Svante Arrhenius suggested that k varies exponentially with 1/T

k = Ae-Ea/RT
Ea is a constant with dimensions of energy A is a constant with the same dimensions as k

k = Ae-Ea/RT
Taking the natural logarithm of this equation gives: ln k = ln A - Ea/RT so that a plot of ln k vs. 1/T should be a straight line with slope of -Ea/R. Many rate constants do follow this behavior.

Arrhenius believed that for molecules to react upon collision, they must become "activated," and the parameter Ea has become known as the Activation Energy

Figure 15.9

Only some collisions occur with enough energy to overcome the activation barrier

Finding the activation energy from 2 data points

Instead of a plot of of ln k vs. 1/T and getting Ea from the slope, you can calculate Ea from: ln k1 = ln A - Ea/RT1 ln k2 = ln A - Ea/RT2 Taking the difference of these two equations: ln (k2/k1) = (Ea/R)[(1/T1 - 1/T2)]

Example: 2HI(g) H2(g) + I2(g)

Rate = k[HI]2 T1 = 500K T2 = 600K k1 = 9.51x10-9M-1s-1 k2 = 1.10x10-5M-1s-1

ln (k2/k1) = (Ea/R)[(1/T1 - 1/T2)]

ln (1.1x10-5/9.51x10-9) = (Ea/8.3145J/molK)*[(1/500K - 1/600K)]

rearrange and solve: Ea = 176kJ/mol

Catalysis
It is not always practical or convenient to increase reaction rates by increasing the temperature. A Catalyst is a substance that speeds up a reaction without being consumed during by the reaction Catalysis - The use of catalysts to speed up reactions without changing the temperature Homogeneous catalysts- catalysts that are in the same phase (e.g. solution or gas) as the reacting molecules Heterogeneous catalysts- catalysts that are in a different phase from the reacting molecules

Catalysts
Catalysts are used in a huge variety of ways because they can enhance reaction rates by many orders of magnitudes! In general, they work by lowering the activation barrier to a reaction. Note that the energies of the reactants and products do not change, only the energy barrier changes. The transition state is stabilized by the catalyst!

Example of a Homogeneous Catalyst

Ethylene Polyethylene (polymerization)

Catalyst: TiCl4/Al(C2H5)3 This is one member of a large class of polymerization catalysts developed by Ziegler and Natta (Nobel Prize in Chemistry, 1965) A lot of research is currently directed toward developing polymerization catalysts that make new polymers with attractive properties (e.g. teflon, kevlar, conductive polymers) (we'll talk more about polymers in chapter 22)

Example of a Heterogeneous catalyst

2N2O(g)

2N2(g) + O2(g)

Figure 15.16: Exhaust gases Figure 15.7: Decomposition of N2O(g) by Pt metal