Sec.

77

petween

CH3 CH3
I I
NaOH + CH,-C-CH, CH,-C-CH, + NaBr
I
Br
I
OH

1-
ordm-and

Solution

text,7
/

-~TBB = ~CTBB (E3-2.1)

(TBB)

3.1.4 Reversible Reactions

.All rate laws for reversible reactions must reduce to the thermodynamic
relationship relating the reacting species concentrations at equilibrium. At lequi-
librium, the rate of reaction is identically zero for all species (i.e., -rA E 0).
That is, for the general reaction

aA+bB ec C + d D (2- 1)
the concentrations at equilibrium are related by the thermodynamic relation-
ship (see Appentdix C).

Thermodynamic
Equilibrium (3- 10)
Relationship

The units of K , are ( m ~ l / d r n ~ ) ~ + ~ - ~ - ~ .

To illustrate how to write rate laws for reversible reactions we will use
the combination of two benzene molecules to form one molecule of hydrogen

Ibid.
 70 Rate Laws and Stoichiometry Chap. 3

and one of diphenyl. In this discussion we shall consider this gas-phase reac-
tion to be elementary and reversible:

2C6H6 <
kB

k-B
' C12HlO +H2
or symbolically,

The specific reaction The forward and reverse specific reaction rate constants, k, and k-, ,
k17 be respectively, will be dejined with respect to benzene.
defined w.r.t.
a particular species Benzene (B) is being depleted by the forward reaction

2c6 H6
kB
' c,, HI0 + H2

in which the rate of disappearance of benzene is

-
rB,forward = kBCi

If we multiply both sides of this equation by -1; we obtain the expression'for

the rate of formation of benzene for the forward reaction:

rB,forward = -kBci (3-11)

For the reverse reaction between diphenyl (D) and hydrogen (H2),

Cl2HlO + H2 k-B > 2C6H6

the rate of formation of benzene is given as
YB, reverse = ~-BCDCH, (3-12)

The net rate of formation of benzene is the sum of the rates of formation from
the forward reaction [i.e., Equation (3-1 l)] and the reverse reaction [i.e., Equa-
tion (3-12)]:

rB rB, net = rB, forward + 'B, reverse

(3-13)

Multiplying both sides of Equation (3-13) by -1, we obtain the rate law for
the rate of disappearance of benzene, -rB :

Elementary
reversible
A.B

-r,=k
[ 2)CA--
(3-14)
 Sec. 3.1 Basic Definitions 79

where

kB
-= K , = concentration equilibrium constant
k-B
The equilibrium constant decreases with increasing temperature for exotlhermic
reactions and increases with increasing temperature for endothermic reactions.
We need to check to see if the rate law given by Equation (3-14) is ther-
modynamically consistent at equilibrium. Using Equation (3- 10) and substitut-
ing the appropriate species concentration and exponents, thermodynamics tells
us that

(3-15)

At equilibrium, -rB = 0, and the rate law given by Equation (3-14) becomes
At equilibrium the
rate law mwt
reduce to an - r B ~ O = kC
equation
consistent with
thermodynamic Rearranging, we obtain
equilibrium

which is identical to Equation (3-15).

A further discussion of the equilibrium constant and its thermodynamic
relationship is given in Appendix C.
Finally, we want to rewrite the rate of formation of diphenyl and hydro-
gen in terms of concentration. The rate of formation of these species must have
the same functional dependence on concentrations as does the rate of disap-
pearance of blenzene. The rate of formation of diphenyl is

(3-16)
L J

Using the relationship given by Equation (2-20) for the general reaction

(2-20)

we can obtain the relationship between the various specific reaction rates,
k , , k,:

(3-17)
 80 Rate Laws and Stoichiometry Chap. 3

Comparing Equations (3-16) and (3-17), we see the relationship between the
specific reaction rate with respect to diphenyl and the specific reaction rate
with respect to benzene is

Example 3-3 Formulating a Reversible Rate Law

The exothermic reaction

Af2B ___) 2D (E3-3.1)

is virtually irreversible at low temperatures and the rate law is

-rA = k,Cy2CB (E3-3.2)

Suggest a rate law that is valid at high temperatures, where the reaction is revers-
ible:

A+2B e2D (E3-3.3)

Solution
These criteria must The rate law for the reversible reaction must
be satisfied
1. satisfy thermodynamic relationships at equilibrium, and
2. reduce to the irreversible rate law when the concentration of one or more of
the reaction products is zero.
We know from thermodynamics that the equilibrium relationship for Reaction
(E3-3.1) as written is

Kc=
c2, with units
- [K,] =
dm3
(E3-3.4)
cAecie

Rearranging Equation (E3-3.4) in the form\

suggests that we try a reversible rate law of the form

-r, = k, [
CACi- g] (E3-3.5)

Equation (E3-3.5) satisfies the equilibrium conditions but does not simplify to the
initial, irreversible rate when C, = 0. Substituting C, = 0 into the equation being
tested yields