Equation 3.43 can be rearranged and integrated for the same two conditions used in Equation 3.

40 to obtain
an expression that describes the concentration of C with time:

Here, k is the first-order reaction rate constant and has units of time_1 (for example, h _1, day_1).
A reaction is first-order when the natural logarithm of concentration data plotted versus time results in a straight
line. The slope of this straight line is the first-order rate constant, k, as illustrated in Figure 3.12.
There are some important things to note about first- and zero-order chemical reactions. First, when comparing
the concentration over time in the two reactions (as shown in the figure), the rate of the first-order reaction
(slope of concentration data versus time) decreases over time, while in the zero-order reaction, the slope
remains constant over time.
This suggests that the rate of a zero-order reaction is independent of chemical concentration (see Equation
3.42), while the rate of a first order reaction is dependent on the concentration of the chemical (see
Equation 3.44). Thus, a chemical whose disappearance follows concentration- dependent kinetics, like first-
order, will disappear more slowly as its concentration decreases.

PSEUDO FIRST-ORDER REACTIONS

There are many circumstances in which the concentration of one participant in a reaction remains constant
during the reaction. For example, if the concentration of one reactant initially is much higher than the
concentration of another, it is impossible for the reaction to cause a significant change in the concentration of
the substance with the high initial concentration. Alternatively, if the concentration of one substance is buffered
at a constant value (for example, pH in a lake does not change because it is buffered by the dissolution and
precipitation of alkalinity-containing solid CaCO3), then the concentration of the buffered species will not
change, even if the substance participates in a reaction. A pseudo first-order reaction is used in these
situations. It can be modeled as if it were a first-order reaction.
Consider the following irreversible elementary reaction:

The rate law for this reaction is

If the concentration of A does not change significantly during thereaction for one of the reasons previously
discussed (that is, ½A0_ ½B0_ or ½A_ ffi ½A0_), the concentration of A may be assumed to remain
constant and can be incorporated into the rate constant, k. The rate law then becomes

where k

0 is the pseudo first-order rate constant and equals k½A0_a. This manipulation greatly simplifies the rate law
for the disappearance of substance B:

If b is equal to 1, then the solution of Equation 3.48 is identical to that for Equation 3.44. In this case, the
pseudo first-order expression can be written as follows: