TEKNIK REAKSI KIMIA LANJUT

SUMMARY CHAPTER 3

COMPLICATED RATE EQUATIONS

Oleh :

Rahmanda Luthfia 1906322796

Departemen Teknik Kimia

Fakultas Teknik
Universitas Indonesia
2020
Chapter 3
Complicated Rate Equation
Chapter 3 deals with many examples of complicated rate equations, namely, those that are
not simple.
Kinetic systems can be classified in several ways, perhaps most generally as either parallel
reactions or consecutive reaction. In paralel reactions a reactant undergoes two or more concurrent
reactions to give different products. The grouping might be expanded to include two or more
reactants undergoing reaction to give a common product. Parallel reaction are also called
competitive reactions.
Consecutive reactions are those in which the product of one reaction is the reactant in the
next reaction. These are also called series reactions. Reversible (opposing) reactions, autocatalytic
reactions, and chain reactions can be viewed as special types of consecutive reaction.
3.1 Integration of the rate equations
Reversible reaction
Scheme I

the simplest reversible reaction

The differential rate equation, according to the law of mass action :

(1)
As the initial conditions (CA = CAo and Cz = 0), thus the mass balance relationship is CAo = CA
+Cz, which is combined with Eq. (1) to give

(2)
At equilibrium (dCA/dt = 0), apllying this condition to Eq. (2) yields (k1 + k-1)CAo=k-1CAo,
where CAo is the equilibrium value of CA :

(3)
Integrated rate equation :
 (4)
𝑘1
When dCA/dt =0, we get k1Cao = k-1Cez or Cez/ CeA = 𝑘−1 = K

Scheme II

Rate equation (If pseudo-first0order conditions don’t apply) :

(5)

Let ; ; ; ∆ defined as the displacement of a

concentration from its equilibrium value. The equilibrium constant is K = k1/k-1 = Cez/ CeACeB.
algerabic combination of these relationship with Eq. (5) :

(6) where (7)

Separation of variable and integration gives the indefinite integral :

(8)
The value of the integration constant is determined by the magnitude of the displacement from the
equilibrium positionat zero time.
Scheme III

If pseudo first order conditions can be established, for example, by setting CoB >> CoA. firtst
order rate constant is ; equilibrium constant is .
Sceme IV
The device of ∆, the displacement from equilibrium, is used in the study of very fast reversible
reactios by relaxation kinetics.
Parallel reaction
Scheme V

Scheme V shows a complex reaction in which a single reactant A undergoes independent,

concurrent reactions to yield two different products.
The rate equation for the loss A :

(9) or (10)
Where k = k1+ k2
Rate equation for product Y :

(11)

Integrated of equation for product Y, Where :

(12)
And similarly for product Z :

(13)
For the case C0y = 0 and c0z = 0 is equal to the ratio of rate constants. The ratio of product
concentrations:

(14)
The ratio of product concentration is equal to the ratio of rate constant, independently of time.
Scheme VI
Describes a reaction system in which two reactants yield a common product.

Te reactant follow first order kinetics, so and , the mass

balance expression is (15).
Combining these equation gives :

(16) or (17)
If k1 >> k2 the Eq. (17) becomes

(18)
k2 is obtained from the terminal linear portion, which is extrapolated back to t=0 to obtain CoB.
with CoB and k2 available, Cb can be calculated and substracted from (Cz∞ -Cz) to yield CA.
finally a plot of ln CA vs. t gives CoA and k1.

Figure 3-1 shows calculated plots of Eq.(17) for hypothetical systems in which k1/k2 has te value
1 and 5.
Scheme VII
Constitutes an equivalent system if the concentration of reagen R is mush larger than the reactant
concentration, so we have pseudo-first order condition.

In scheme VII the reactant A and B compete from reagent R. There may be additional product.
Scheme VIII

Consider the case of parallel first order and second order.

The differential rate equation is

(19)
Define r = k2/k1, and use Eq.(19) to get

(20)
Integrated rate equation :

(21)
Scheme VIII applies also to a system that includes a reagent if the reagent concentration is much
larger than CoA.
Consecutive Reaction
Scheme IX
Complex reaction that occurs widely

This consists of two consecutive irreversible first order (or pseudo first order) reactions. The
differentian rate equation are :
 (21)

(22)

(23)

The reactant A follows a first order rate equation : (24)

The dependence of CB use the integrating factor method

And multiply both sides by 𝑒 𝑘2𝑡 , the integrating factor.

(25)
Notice that

(26)
Comparing Eqs. (25) and (26)

Integrated to yield

The constant is determined by initial conditions, Suppose CB = 0 at t = 0; Constant = −𝐶𝐴0 𝑘1 /(𝑘2 −

𝑘1 )

(27)

For the initial condition 𝐶𝐵0 = 0, 𝐶𝑐0 = 0, the mass balance (28)
Substituting Eqs. (27) into (28) and rearranging yields

(29) or (30)
Eqs. (27) and (29) are inapplicable in the special case k1 = k2
Figure 3-2 shows the dependence of CA, CB, CC on time for a hypothetical system for which
k1/k2 = 4.

Figure 3-3 is the same type of plot for a system having k1 / k2 = ¼.

In this case the concentration of B is at all times less than that in fig. 3-2.B is a more reactive
intermediate in fig. 3-3. The time at which CB reaches its maximum value is found by setting
dCB/dt = 0; the result is

(31)
The method of evaluation of the rate constants for this reaction scheme will depend upon the types
of analytical information available. This depends in part upon a nature of the reaction, but it also
depends upon the contemporary state of analytical information. Titrimetry was a widely applied
means of studying reaction kinetics. Titimetric analysis is not highly sensitive, nor is it very
selective, but it is accurate and has the considerable advantage of providing absolute
concentrations. When used to study A → B → C system in which the same substance is either
produced or consumed in each step, titration results yield a quantity F = CB + 2CC with the
equation:

(32)
Define r = k2/ki; d = k1.t, the eq. (32) becomes :

(33)
Instrumental methods of analysis provide different measures of the progress of reaction. Consider
this kinetic system as observed by absorption spectroscopy. Beer’s law applied to the system gives
(34)
Aλ = solution absorbance at a single wavelenght.
Scheme X
Constitutes an extension of the preceding discussion

The differential rate equation are

(38) (40)

(39) (41)
for the initial condition Cc = 0 at t = 0

(42)
The concetration of D is then found from the mass balance
(43)
 (44)
Scheme XI

R is a common reagent. The alkaline hydrolysis of a diester is an example.

A = diester ROOC-(CH2)n-COOR; B = the half estre ROOC-(CH2)n-COO-; R=OH-.
Simple second order reaction

The differential rate equation is and the mass balance is .

Eliminating CA between these equation and integrating give the usual second order integrated
equation\

(45)
Differential equation where k is a function of k1 and k2

(46)

3.2 Other methods of analysis

Measurement of rate
Scheme XII

The differential rate equation for the loss of A is

(47) which can be written

• emphassizing that the rate depends upon the concentration. Rearranging gives

(48)
If CA and CB can both be measured as functions of time, a plot of v/CA vc. CB allows the rate
constants to be estimated.

Simplication of the experimental kinetics

It may be posiible to convert a very complex reaction into a less complex system by appropriate
choice of reaction condition or analytical methods. Here are some possibilities.
1. Use of the isolation or pseudo order technique
2. Study of reversible reactions close to equilibrium
3. Neglect the terminal stages of the reaction
4. Neglect of the intial stages of the reaction
5. Use of an intermediate as a astarting reactant
6. Mimicking the reactant with a derivative or analog that cant undergo the full complexity of the
reaction
7. Change of reaction conditions to minimize kinetic complications
8. Choice of initial conditions
9. Exploitation of analytical selectivity
Elimination of the time variable
For parallel reaction the following technique is often helpful. We illustrate with scheme V, writing
for the products

Dividing one of these equations by the other gives dCy/dCz = k1/k2, the time variable canceling.
Integration yields

(49)
Scheme XIII
More complex example. Suppose that reactant B is consumed only in the second order reaction

The differential rate equations are

(50)

(51)
Dividing (50) by (51)

(52)
Integration gives

(53)
Rate constant ratio

(54)
From eq. (54) and measurements of CA and CB, the ratio k1/k2 can be obtained. Solution of
eq.(53) for CA, subtitution into Eq (51) and integration gives

(55)
Replacement of time with an area variable
We introduce the technique by considering the second-order reaction of A and B, for which the
differential rate equation is

(56)

Define a variable 𝜃 by eq.(57)

(57)

d 𝜃 = CBdt, combining this equality with eq. (56)

(58)

Integrated (59)
Scheme XIV

Differential rate equations

 (60); (61); (62)
Using the definition of (57) converts Eq. (62) to

(63)
Integrated equation of (60) using another approach and varibel θ.

Again using the definition (57)

(64)
The laplace transformation
Linear differential equation with constant coefficient can be solved by a mathematical technique
called Laplace Transformation. Zero-order or first order reaction give rise to differential rate
equation of this type, and the Laplace transformation often provides a simple solution.
Let y=F(t) be a function of t. Then the Laplace Transform of F(t) :
(65)
Laplace transformation converts a function of t, F(t) into a function of s, f(s) where s is
transformation variable.

(66)
f(s) = Laplace transform of F(t).
Suppose F(t) = a where a is a constant. Then :

Let 𝐹(𝑡) = 𝑒 −𝑎𝑡 ,

Table 3-1 gives a small selection of Laplace transform.
Application of the definition shows that Laplace shows that the Laplacetransform is a linear
operator, this property is represented in (67) and (68)

(67)
(68)
The laplace transform of a derivative dy/dt is found by application of Equation (65) and integrated
by part

(69)
yo is the value of y when t=0 and ỹ is the transform of y.
illustration for a simple first order reaction, differential rate equation :

Laplace transform :
We transform this for the transform CA

Transform no.4 in the table 3-1, with a = -k, we obtain

a transformation that arises in the solution to a problem cannot be found in table of transform. In
such a case it is often possible, by algebraic manipulation, to place the transform is placed in a
form that permits the inverse transform to be taken. We refer to as the general partial fraction
theorem. This theorem applies to a transform that can be written :

(70)
H(s) and G(s) are polynomials in s, the degree of H(s) being less than that of G(s). if G(s) can be
written in the form :
(71)
where the a1, a2, ….., an must all be different, then

(72)
H(ar) is the function H(s) with s set equal to ar (in each term of the sum). Similary, In the
denominator, s is set equal to ar in G(s).
We illustrate with a numerical example. Suppose

or
This transform does not appear in tabel 3.1. because it has the form of Eqs. (70) and (71), with a1
= 0, a2 = -5, we apply Eq.(72) :

Using no. 1 and 4 of table 3-1, we find :

As an example, we take kinetic scheme IX, for which the differential rate equation are :

(73)
 (74)
Taking the transforms of these equation gives

(75)

(76)
initial conditions are cA = 𝑐𝐴0 and cB = 0 at t = 0, equation for ĉB :

(77)
The inverse transform is given by No. 6 in Table 3-1:

(78)
scheme XIV with reactions :

The differential rate equations are

(79)

(80)
where k = k-1 + k2, the transforms gives eqs.(81) and (82)
(81)
(82)
Solving eq.81 for ĉA gives

Substituted into Eq.(82)

(83)

(84)
Where :
(85)
(86)
With no.6 of table 3-1, the inverse transformation yields :
 (87)
To find cA we subtituted Eq.(84) into (82) :

(88)
Apply the general partial fraction theorm, eq.(72) to (88), With a1 = -α, a2 = -β :

(89)
Using no.4 of table 3-1 :

(90)
Scheme XV
Constitutes two consecutive reversible first order reaction

The differential rate equation are

(91) (92) (93)

With the initial condition . The mass balancev relationship
The Laplace transforms

(94)

(95)
Equation of (94) is solved for cA, and this is substituted into (95) which is solved for cB
 (96)
Where :

(97)

(98)
Inverse transform

(99)
Solve eq. 94 for cB, substituted it into (95) and solve for cA. result :

(100)

Where and 𝛼 and 𝛽 is (97) and (98). Inverse transform

(101)
Combining the definition of m with (97) and (98)

(102)
The concentration of cC is easily found by substituting eq.(99) and (102) into the mass balance
expression:

(103)
Secular Equations and Eigenvalues.
Systems of reversible first order reactions lead to sets of simultaneous linear differential equations
with constant coefficients. A solution may be obtained by means of matrix formulation used in
quantum mechanics and vibrational spectroscopy. First, we consider scheme I (single reversible
first order reaction)

The differential rate equations are

 (104)
(105)
′
Where 𝑐𝑖 = 𝑑𝑐𝑖 /𝑑𝑡. In matrix notation these equations become

(106)
(106) is simple first order equation, whose solution

Where boldface symbols represent matrices.

(107)
Where λ is parameter that is, at present, an unknown function of the elementary rate constants.
General solution are then constructed as linear combinations of particular solutions; for this
problem,

(108)

From (107) : (109)

Substituting (107) and (109) into (1040 and (1050 yields the simultaneous homogeneous algebraic
equations.

(110)
These equations are satisfied if JA = 0, JZ = 0, but this trivial solutions is of no interest. equation:

(311)
(311) is the secular equation for this problem. Expansion of the determinant gives a polynominal
in 𝜆 that is called the characteristic equation :

(112)

These equations are not independent, it is not possible to solve uniquely for individual JA, JZ values;
only ratios can be obtained, as follows:
(113)
(114)
Eq.(113) and (114) are substituted into the general solution eq.(108) :
 (115)
Initial conditions, cA = coA, cZ = 0 at t =0, using this conditions allows JA1 and JA2 to be evaluated

(116)
Where K = k1/k-1, the equilibrium constant for the reaction. The solution is

(117)
To put this into a more familiar form, let t = ∞; then cA = ceA , ceA = coA/(1+K), and

When , giving :

(118)
Which is identical to eq. (3-4)
The preequilibrium assumption
Scheme XVI
Scheme XVI is more difficult to analyze are any of kinetic schemes treated earlier in this chapter
because it include a second order reaction

Rate of reaction, expressed as the rate of product formation

(131)
First consider the nature of equilibrium from the kinetic viewpoint if the reaction

(at thermodynamic equilibrium)

(132)
The equilibrium constant K is given by , we obtain

(133)
The equilibrium assumption is applied to scheme XVI. From above consideration,
which combined with (131)

(134)
Scheme XVII
Fast preequilibrium step. Proton transfers constitute a very important class of fast preequibria, as
illustrated by scheme XVII for acid catalyzed ester hydrolysis

The term fast and low are relative (the hydrolysis step is followed by another fast proton transfer,
but this has no effect on the rate of hydrolysis).
In other to obtain a better sense of the range of validity of the equilibrium assumption, consider
scheme XIV, for which a quantitative description was achieved earlier by means of Laplace
transform.

Combining (87) and (90), Exact solution for the ratio cB / cA :

(135)
From (85) and (86), , The equilibrium assumption gives
for this ratio of concentrations :

(136)
Fig. 3-9 shows plots of (135) and (136) for some hypothetical systems.
Scheme XVIII
Cyclic kinetic scheme

The equilibrium constants

It follows that K1K2K3 = 1, and, therefore

(143)
The rate of change of Cc is

Equilibrium assumption cA = K1cA; initial condition ; mass balance 𝑐𝐴0 =

𝑐𝐴 + 𝑐𝐵 + 𝑐𝑐 . cA and cB can be eliminated from the rate equation to give.
 (138)
Where

The Steady-State Approximation.

Scheme XIV for the example, letting differential rate equations are

(139) (140) (141)

Assumption cB is steady state and 𝑐𝐵′ = 0, so :

(142)
Rate equations for 𝑐𝐴′ and 𝑐𝐶′ are :

(143)
The reaction displays simple order kinetics, with the observed first order rate constant being equal
to k1k2/(k1 +k2)
Evidently cB will be small relative to (cA + cC) if (k1+k2) > k1. Then B plays the role of a “reactive
intermediate” in the overall reaction A →C. However the condition c’B = 0 is a sufficient but
unnecessary condition foe Eq. (142) to hold. From (140) we obtain

Scheme XIX
When reaction other than first order processes are included in the kinetic scheme, reactant
concentrations may appear in the denominator of the rate equation.

Rate equation
Applying the steady state approximationto C gives

(144)
Equation(144) substituted in the rate equations for A and Z yield

(145)
Second order rate constant :

(146)
Scheme XX
The simplest kinetic scheme that can account for enzyme catalyzed reactions, where E represents
the enztme, S is the substrate, P is a product, and ES is an enzyme substrate complex.

The steady state approximation to the complex ES

(147)
Mass balance expression for the enzyme is
(148)
Combined with (147) to eliminate [E] :

(149)
The rate reaction :

or
Which is usually written

(150) (michelis menten eqution)

Vm= maximum velocity
Where
 (151)
The double reciprocal form (152) is called the Lineweaver-Burk plot in enzyme kinetics

The Michelis constant has the units of a dissociation; however, the dissociation constant of the
enzyme-substrate complex is k-1/k1, which is not equal to Km unless k1>>k2.
The equilibrium and the steady state approximation for the intermediate concentration :

(153) (154)
The equilibrium description would be very accurate, but the wide variations in cB would vitiate the
steady state description. There appear to be three classes of practical behavior, as defined by these
conditions :

Numerical Integration.
In these circumtances we must fall back on technique that are essentially curve fitting procedures
and that involve some degree of approximation.
we take the simple first order rate equation as an example, namely, dc/dt = -kc, let c=y, t=x, so :

(155)
We approximate differential with increments and all subsequent expression are, therefore,
approximate. equation 155 becomes :

(156)
A uniform time interval ∆x=h is taken. The only information needed is an initial value (x0,y0) and
an estimate of k. Define :
(157)
(158)
From (156) and (158) we have ∆y=-hky, combined with (156) and (157) gives :
Euler’s method is used to evaluate ∆y/∆x at x0. From eq. (156), this give (∆y/∆x)0 = -ky0, which
used in (159), yields
(160)

The grapical problem is shown in fig 3-11.

We have (∆y/∆x)0 = -ky0 and (∆y/∆x)1 = -ky1, so (∆y/∆x)av = -k(y0+y1)/2, where (∆y/∆x)av is the
mean value. We know y0 but y1 is at present unknown. However, an estimate is available in Eq.
(3-160), giving

(161)
Equation (161) is then used in (159):

(162)
Eq. 162 should be compare with eq. 160
Complex reactions require the solution of simultaneous differential equations, and the Runge-
Kutta procedure is applicable to these problems. To illustrate the method, scheme XIV will be
used. The rate equations are, in incremental form,

(163)
Where x = t, y = cA, z = cB, k = k1+k2
Proceeding as before, we define h = ∆x, y1 –y0 = ∆y, z1 – z0 = ∆z, and obtain, as in the earlier
development,

(164)
A second order treatment will be given, the derivatives being evaluated at (x0,y0,z0) and (x1,y1,z1).
From eq.163

(165)
The quantities y1 and z1 are evaluated with eq.164 at Po. These are used in eq.166. then the means
are calculated with

(167)
Equations (167) are used in eq. 164, yielding :

(168)
Monte Carlo Simulation.
The Monte Carlo or stochastic method for constructing concentration-time curves is based on the
statistics of random events applied to large numbers.
To illustrate the technique we will treat Scheme IX :

For Scheme IX we need three grids, one for each species:

To see the connection between this stochastic process and a chemically reacting system, consider
the first step of Scheme IX. For this first-order reaction, the chemical system is described by

(169)
The analogues equations in the simulation systems are

(170)
Supossing the simulation mimmics the chemistry, then
(171)
In the same way we write for the second dtep of the reaction
(172)
With 171, 172, and the definiton r = k1/k2, equation (24) and (27) for cA and cB become, for the
simulation,

(173)

(174)
The smooth lines in figure 3-12 were calculated with eq. 173 and 174.
Scheme XXII
Kinetic scheme that include both first-order and second order reactions possess an ambiguty
related to the different dimensions of the rate constant

In grid form

Following schaad, we write

The chemical and stochastic concentrations are reated ,etc. combining these equations
and equating the chemical and stochastic rate ratios give

(175)
Noted that 2n1 is the total number of selections made on grids A and B in one cycle, n1 being made
on grid A and n1 on grid B.
Analog Simulation
Before there were small digital computers, there were small analog computers. An anaolog
computer is a device that can mimic mathematical equations with physical processes. Most analog
computers use electrical circuit
Those circuits include components that carry out arithmetic operations, differention, and
integration. They can be assamled to model a postulated kinetic shceme by “patching” together
components that build up circuits analogous to differential rate equations describing the schemes.
The method is quite effective, but is not widely used now because of the ubiquity of digital
computers.
3.3 The kinetic scheme
Model Building
In a general way a kinetic study of reaction mechanism includes these 4 components:
• Experimental kinetics
• Determination of the rate equation
• Writing the kinetic scheme
• Proposal of transition state structures, stereo chemistries, and energetics.
A postulated kinetic scheme is a model or hypothesis. In accord Occam’s razor, the model should
be no more complex than is required to account for the experimental observations.
1. Background information on the reasonable and expected chemistry of the system.
Knowledge of the pertinent literature is valuable. In deciding whether to write an elementary
reaction as either a reversible or an irreversible reaction, we take the practical view that if the
reverse reaction is negligibly slow on the experimental time scale, the reaction is essentially
irreversible. Consider the alkaline hydrolysis of an ester, for which the rate equation is

An abundance of mechanistic information in litelature suggest this scheme:

Scheme XXIII
Alkaline solution of the carboxylic acid and alcohol does not generate the ester and that the
postulated tetrahedral intermediate can not be detected. Thus, overall reaction is irreversible and
the intermediate is present at very low concentration. These considerations lead to Scheme XXII.
2. Direct detection of an intermediate
When acetonitrile solutions of acetyl chloride and N-methylimidazole are mixed, the absorbance
of the resulting solution is much greater than that calculated for the sum of reactants. On the other
hand, when acetonitrile solutions of acetic anhydride and N-methylimidazole are mixed, no excess
absorption is observed. This considerations lead to Scheme XXIII.

A general treatment of Scheme XXIII requires specifications of the detailed nature of k’A and k’I
is too complicated to be practical use. However, several important special cases may arise from
operation of the ratio k1/k-1, the behavior of apparent rate constant k’A and k’I, the relative
magnitudes, and nature ROH. These cases are outlined in scheme XXIV
3. Indirect detection of an intermediate
The overall reaction of hydroxylamine with a carboxylic acid derivative yields a hydroxamic acid
as the product.

(176)
In this case the intermediate is O-acetylhydroxylamine, which subsequently reacts with
hydroxylamine to form the hydroxamic acid.
Scheme XXV

4. Kinetic evidence for a common intermediate

Suppose a series of related reactants each separately reacts with a common reagent, and rates of
product formation are the same for each reactant:
Scheme XXVI
It is reasonable inference that, if kx = ky = kz, these rate constants all describe the same reaction,
in this example of B- with common intermediate A+:
Scheme XXVII

5. Concentration-time curves
Figure 3-14 shows an induction period in the reaction of carbon suboxide(O=C=C=C=O) with
triethylamine. This reaction is complex and not yet understood, but clearly this kinetic behavior of
a strongly absorbing product is a key observation. The length of the induction period, the maximum
rate of product formation and the final product concentration are all related to the triethylamine
concentration.

6. Dependence of apparent constant on concentration

We Continue consideration of Scheme XXII by making chemically reasonable tentative solection
of form k’A and k’I. First, consider the acetyl chloride-alcohol reaction. The observed reaction:

(177)
The hypothetical rate equation is then
the experimental rate equation is

(178)
Eq. 178 suggest that a plot of Kobs/[ROH] vs [N] will be linear. Because the conversation to the
intermediate is quantitative, [N] = [N]o – [AX]o.
Turning to the acetic anhydride-alcohol system, it is inferred that k1/k-1 is close to zero (Scheme
XXIV). Rate of equation for the loss of anhydride:

The assumption is made that all of the H+ produced in the acetylation is accepted by X- (acetate);
then [X-] = 0, so this becomes

By hypothesis k’A = kA + kAN[N], the experimental rate equations is –d[AX]/dt = kobs =[AX], so

If in a series of experiments the catalyst concentration is held constant while the alcohol
concentration is varied :

(179)
whereas if [ROH] is kept constant and [N] is varied :

(180)
k1 and kA were not significantly different from zero. All of these rate equations can be succinctly
expressed in the form of Scheme XXVIII.
Scheme XXVIII

Kinetic equivalence of rate terms

Supposean experimental rate
(181)
Where HA is a weak bronsted acid. Because of the protonis equilibrium

. Ew. 181 can also be written as

 (182)
Another example is a second -order term containing the concentration of an acid and a base, say
(183)
This is kinetically equivalent to

Microscopic Reversibility and Detailed Balance

Elementary reversible reaction

Differential rate equation :

At equilibrium v = 0, the chemical fluxes in the forward and reverse directions are equal, and we
write

(185)
where K is the equilibrium constant of the reaction
Scheme XVIII

or
where Ki = ki/k-i , thus only five of six rate constants are independent.
In a system of connected reversible reactions at equilibrium, each reversible reaction is
individually at equilibrium.
Detailed balance is a chemical application of the more general principle of microscopic
reversibility, which has its basis in the mathematical conclusion that the equations of motion are
symmetric under time reversal.
In the field of chemical kinetics, this principles in these equivalent forms:
1.The transition state of an elementary reversible reaction in the forward direction is identical to
the transition state in the reverse direction, or
2.The mechanism of a reversible reaction in the rearward direction is identical to the mechanism
in the forward direction run backward.
If the Scheme XVIII is possible, but scheme XXIX is impossible, because B is formed directly
from A, whereas A can only be regenerated from B via C, which is a different mechanism.
Scheme XXIX

The principle does not rule out of the possibility of more than one route
(mechanism) between initial and final states, provided that at equilibrium detailed balance applies
to all routes.
Detailed balancing can provide quantitative arguments by means of relationship like 186.we take
an example the hydrolysis of 𝛿-thiovalerolactone (L) catalyzide by imidazole (lm), for which the
Scheme XXX was proposed, IH being an intermediate.
Scheme XXX

The irreversible k3 is irrelevant to the following argument, which is based on the equilibrium state.
Proceeding to define equilibrium constants as K1 = k1/k-1 = [IH]/[ImH][L] and so on, we obtain
the identity

Or , because K2 and K4 are acid dissociation constants,

(187)
In the original quantitative treatment of the pH dependence of the kinetics, it was necessary to
make the assumption that k3K2 << k1[H+]. From Eq. (187), this means that

or
These two inequalities are inconsistent conditions.