TYPES OF CHEMICAL REACTION RATES

The speed of a reaction is expressed in terms of its rate which is equal to some measurable quantity that is
changing with time.
The rate of a chemical reaction is measured by the decrease in concentration of a reactant or an increase in
concentration of a product in a unit of time.
change in concentration of a species [reacants]
Generally speaking, Rate
time interval t

When writing rate expressions, they can be written in terms of

reactant disappearance or product appearance.
* Rate is not constant, it changes with time. Graphing the data
of an experiment will show an average rate of reaction.

Time [NO2] [NO] [O2]

(s)
0 0.1000 0.0000 0.0000
50 0.0079 0.0021 0.0011
100 0.0065 0.0035 0.0018
150 0.0055 0.0045 0.0023
200 0.0048 0.0052 0.0026
250 0.0043 0.0057 0.0029
300 0.0038 0.0062 0.0031
350 0.0034 0.0066 0.0033
400 0.0031 0.0069 0.0035

1. Instantaneous Reaction Rate which is simply the rate

at a given instant of time, hence its name! You probably know how to do this from math classespecially
if you are currently enrolled in Pre-Calculus or Calculus. Go ahead; its OK to show off! Examine the graph
on the previous page. Note the shapes of the curves in relation to the concentration data presented for each
substance. Note the slope of each of the lines drawn
tangent to a given curve.

To determine the value of the rate at a particular instant

of time, known as the instantaneous rate, simply
compute the slope of a line tangent to the curve at that
point in time. Be particular with regard to your
vocabulary when describing how to do this process.
Writing, take the tangent earns no points. Why
not?

Shall we practice?
Use this technique to determine the instantaneous rate
for the reactant at 10 s and at 20 s.
Use this technique to determine the instantaneous rate
for the product at 10 s and at 20 s.
What has happened to this system at 60 seconds? Practice determining the instantaneous rate for both
substances at 20 minutes and 30 minutes.

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions 4

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2. Relative Reaction Rate is expressed as the change in concentration of a reactant per unit time or
time
You should focus either on the disappearance of reactants or the appearance of products
rate of of a reactant is always negative
rate of of a product is always positive

Also, the word relative here doesnt refer to family members, it refers to terms that relate to each other in
the context of a given chemical system.

Consider the reaction for the decomposition of nitrogen dioxide once again:
2 NO2(g) O 2(g) + 2 NO(g)

A cursory analysis of the stoichiometry of the equations reveals that oxygen gas can appear only half as
rapidly as the nitrogen dioxide gas disappears while NO gas appears twice as fast as oxygen appears.

The simplest way to obtain relative rate expressions is to place a one over each coefficient in the balanced
equation (if a coefficient is missing, it is understood that its coefficient is 1).

Next, apply the appropriate algebraic sign () for reactants since they are disappearing as time goes by, (+)
for products since they are appearing as time goes by. Always respect the algebraic sign AND respect the
stoichiometry.

Thus,
1 NO 2 O2 1 NO
Initial Rate of Reaction = = + = +
2 t t 2 t
Of course you can change these once the ratio is set if you have an aversion to fractions. Simply multiply
ALL the terms by the same factor to eliminate the fractions. In this case, multiply each term by 2. So, you
might prefer 1 : +2 : +1

Shall we try another? Consider this reaction and write all the relative rate terms for the reactants and
products.
4 PH3(g) P4(g) + 6 H2(g)

1 PH 3 P4 1 [ H 2 ]
Rate = = =
4 t t 6 t

Its OK to shorten initial rate of reaction to simply rate. Its OK to leave the + off a coefficient. We are
doing it here for emphasis! Again, you may prefer to multiply through to eliminate the fractions, but you should
work on your prejudices against them! (I still campaign that using the fractions is easier.)

3 [ PH 3 ] 12 P4 2 [ H 2 ]
Rate = = =
12 t 12 t 12 t

[ PH 3 ] P4 [ H 2 ]
which becomes Rate = 3 = 12 = 2
t t t

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions 5