Rate Law for Opposing Reactions of Ist Order and IInd Order

A reaction will be called as the opposing or reversible reaction if the reactants react together to
form a product and the products also react to yield the reactants simultaneously under the same conditions.
In a simple context, we can say these reactions proceed not only in the forward direction but also in
the backward direction. These reactions can be classified into the following categories based upon the kinetic
order of the reactions involved.
 First Order Opposed by First Order
In order to understand the kinetic profile of first-order reactions opposed by the first order, consider
a general reaction in which the reactant A forms product B i.e.

𝑘𝑓 (17)
𝐴 ⇌ 𝐵
𝑘𝑏
Now, if kf ⋙kb, kb can be neglected. However, kf and kb have comparable values, a rate law depending upon
both the constants can be written. To do so, suppose that a is the initial concentration of the reactant A and x
is the decrease in the concentration of A after ʻtʼ time. The concentration of the product after the same time
would also be equal to x. Hence, the rates of forward reaction (Rf) and backward reaction (Rb) can be given
as:

𝑅𝑓=𝑘𝑓[𝐴]=𝑘𝑓(𝑎−𝑥) (17)

𝑅𝑏=𝑘𝑏[𝐵]=𝑘𝑏𝑥 (18)

The net reaction rate i.e. rate of formation of the product can be given as

𝑑𝑥 (19)
=𝑘𝑓(𝑎−𝑥)−𝑘𝑏𝑥
𝑑𝑡
However, when the equilibrium is attained, the rate of forward reaction will be equal to the rate of backward
reaction i.e. Rf = Rb. Therefore, the will take the form

𝑘𝑓(𝑎−𝑥𝑒𝑞)=𝑘𝑏𝑥𝑒𝑞 (20)

Where xeq is the concentration of product B or the decrease in the concentration of reactant A at equilibrium.
Now putting the value of kb from equation (20) into equation (19), we get

𝑑𝑥 𝑘(𝑎−𝑥 ) (21)
𝑓𝑒𝑞
( − )
=𝑘𝑓 𝑎−𝑥 𝑥
𝑑𝑡 𝑥𝑒𝑞

𝑑𝑥 ()𝑎−𝑥 𝑒𝑞 (22)
( − )
=𝑘𝑓[𝑎−𝑥 𝑥]
𝑑𝑡 𝑥𝑒𝑞
or

𝑑𝑥 (𝑎−𝑥)𝑥 − ()
𝑎−𝑥 𝑥 (23)
𝑒𝑞𝑒𝑞
𝑥
=𝑘𝑓[ ]
𝑑𝑡 𝑒𝑞
(24)
𝑑𝑥 𝑎𝑥 −𝑎𝑥 𝑘𝑎(𝑥 −𝑥)
𝑒𝑞 𝑓𝑒𝑞
=𝑘𝑓 =
𝑑𝑡 𝑥𝑒𝑞 𝑥𝑒𝑞

or
𝑥𝑒𝑞 (25)
𝑑𝑥=𝑘𝑓𝑎𝑑𝑡
(𝑥𝑒 𝑞−𝑥)

Integrating equation (25), we get

−𝑥𝑒𝑞ln(𝑥𝑒𝑞−𝑥)=𝑘𝑓𝑎𝑡+𝐶 (26)

Where C is the consta n (26), we get

(27)

Using the value of C

(28)

or

(29)

(30)

Using equation (30), by measuring simple

quantities like a, t, xe
𝑘 𝑘𝑓(𝑎−𝑥𝑒𝑞) (31)
𝑏=
𝑥𝑒𝑞

𝑘(𝑎−𝑥 ) 𝑎𝑎 𝑥 (32)
𝑓𝑒𝑞 𝑒𝑞
𝑘𝑏= =𝑘𝑓( − )=𝑘𝑓( −1)
𝑥𝑥𝑥𝑥
𝑒𝑞 𝑒𝑞 𝑒𝑞 𝑒𝑞

Now putting the value kf from equation (30) in equation (32), we get

1 𝑥 𝑥 𝑥 (33)
𝑒𝑞𝑒𝑞𝑒𝑞
𝑏=( n )− n
𝑡 𝑥𝑒𝑞−𝑥 𝑎𝑡 𝑥𝑒𝑞−𝑥
𝑘 l l

Hence, the value of the rate constant for backward reaction can also be obtained just by measuring t, xeq and x;
or in other words, the kf eventually yields the kb also.
 Alternatively, the values of kf and kb can also be obtained a slightly different route. Rearranging
equation (30), we get
𝑎𝑘 1 𝑥 (34)
𝑓 𝑒𝑞
= ln
𝑥𝑒𝑞 𝑡 𝑥𝑒𝑞−𝑥

Also rearranging equation (20), we have

𝑘𝑎 (35)
𝑓
=𝑘𝑏+𝑘𝑓
𝑥𝑒𝑞

Equating the right-hand sides of equation (34) and (35), we get

1 𝑥 (36)
𝑒𝑞
ln =𝑘𝑏+𝑘𝑓
𝑡 𝑥 −𝑥
(37)

or

(38)

Equation (37) and (38

𝑥𝑥𝑒𝑞𝑒𝑞
Figure 6. The plot of ln and log vs time for first order opposed by the first order.
𝑥𝑒𝑞−𝑥 𝑥𝑒𝑞−𝑥

Now, finding kf +kb from slope and kf/kb from equilibrium constant, kf and kb can easily be obtained from the
𝑥𝑒𝑞−𝑥 𝑥𝑒𝑞−𝑥
elimination method. It should also be noted that if plot ln and log , the slopes will become negative.
𝑥𝑥𝑒𝑞 𝑒𝑞
  First Order Opposed by Second Order
In order to understand the kinetic profile of first-order reactions opposed by second-order, consider
a general reaction in which the reactant A forms product B and C i.e.

𝑘𝑓 (39)
𝐴 ⇌ 𝐵+𝐶
𝑘𝑏
Now, if kf ⋙kb, kb can be neglected. However, kf and kb have comparable values, a rate law depending upon
both the constants can be written. To do so, suppose that a is the initial concentration of the reactant A and x
is the decrease in the concentration of A after ʻtʼ time. The concentration of both the products after same time
would also be equal to x. Hence, the rates of forward reaction (Rf) and backward reaction (Rb) can be given
as:

𝑅 =𝑘[𝐴]=𝑘(𝑎−𝑥) (40)

(41)

The net reaction rate

(42)

However, when the e the rate of backward

reaction i.e. Rf = Rb. T

(43)

Where xeq is the con tion of reactant A at

equilibrium. Now put

(44)
𝑑𝑡 𝑥𝑒𝑞

𝑑𝑥 ()𝑎−𝑥 𝑒𝑞 2 (45)
( − )
=𝑘𝑓[𝑎−𝑥 2
𝑥]
𝑑𝑡 𝑥𝑒𝑞

or
(𝑎−𝑥)𝑥2 − 𝑎−𝑥 𝑥2
𝑑𝑥 𝑒𝑞𝑒𝑞 () (46)
=𝑘𝑓[ 2
]
𝑑𝑡 𝑥𝑒𝑞
2 2 (47)
𝑑𝑥 𝑎𝑥𝑒𝑞−𝑥𝑥𝑒𝑞−𝑎𝑥2+𝑥𝑒𝑞𝑥2 𝑒𝑞
𝑑𝑡 =𝑘𝑓[ 𝑥2 ]
or
 123

𝑥2 (48)
𝑒𝑞
( 22
𝑑𝑥=𝑘𝑓𝑑𝑡
𝑎𝑥𝑒𝑞−𝑥𝑥𝑒𝑞−𝑎𝑥2+𝑥𝑒𝑞𝑥2)

Integrating equation (48), and then rearranging

𝑥𝑒𝑞 𝑎𝑥𝑒𝑞+𝑥𝑒𝑞(𝑎−𝑥𝑒𝑞) (49)

𝑘𝑓=ln
𝑡(2𝑎−𝑥𝑒𝑞) 𝑎(𝑥𝑒𝑞−𝑥)

Using equation (49), the rate constant for the forward reaction can easily be determined by measuring simple
quantities like a, t, xeq and x. Now, we know that the equilibriumconstant for the first order opposed by
second-order will be

[𝐵][𝐶] (50)
𝐾=
[𝐴]

also

(51)

Now putting the valu kb, we get

(52)

Hence, the value of th measuring t, xeq and x

and the equilibrium c
 Second Orde
In order to u first order, consider a
general reaction in w

𝑘𝑓 (53)
𝐴+𝐵 ⇌ 𝐶
𝑘𝑏
Now, if kf ⋙kb, kb can be neglected. However, kf and kb have comparable values, a rate law depending upon
both the constants can be written. To do so, suppose that a is the initial concentration of both the reactant A
and B; while x is the decrease in the concentrations of both reactants after ʻtʼ time. The concentration of the
product after the same time would also be equal to x. Hence, the rates of forward reaction (Rf) and backward
reaction (Rb) can be given as:

𝑅𝑓=𝑘𝑓[𝐴][𝐵]=𝑘𝑓(𝑎−𝑥)2 (54)

𝑅𝑏=𝑘𝑏[𝐶]=𝑘𝑏𝑥 (55)
The net reaction rate i.e. rate of formation of the product can be given as

𝑑𝑥 (56)
=𝑘𝑓(𝑎−𝑥)2−𝑘𝑏𝑥
𝑑𝑡
However, when the equilibrium is attained, the rate of forward reaction will be equal to the rate of backward
reaction i.e. Rf = Rb. Therefore, the equation (56) will take the form

𝑘 (𝑎−𝑥 )2=𝑘 𝑥 (57)

𝑓 𝑒𝑞 𝑏 𝑒𝑞

Where xeq is the concentration of the product C or the decrease in the concentration of reactant A or B at
equilibrium. Now putting the value of kb from equation (57) into equation (56), we get
2 (58)
𝑑𝑥 𝑘(𝑎−𝑥
𝑓𝑒𝑞 )
=𝑘𝑓 𝑎−𝑥 − 𝑥

(59)

or

(60)

(61)

(62)

𝑎𝑥𝑒𝑞+𝑥𝑥𝑒𝑞−𝑎𝑥−𝑥𝑒𝑞𝑥 (63)
=𝑘𝑓[ ]
𝑑𝑡 𝑥𝑒𝑞

or
𝑥 𝑒𝑞 (64)
2𝑑𝑥=𝑘𝑓𝑑𝑡
(𝑎2𝑥𝑒𝑞+𝑥2𝑥𝑒 𝑞−𝑎2𝑥−𝑥𝑒𝑞𝑥)

Integrating equation (64), and then rearranging

𝑥𝑒𝑞 𝑥𝑒𝑞(𝑎2−𝑥𝑒𝑞𝑥) (65)

𝑘𝑓=ln 2
𝑡(𝑎 −𝑥𝑒𝑞2) 𝑎2(𝑥𝑒𝑞−𝑥)
Using equation (66), the rate constant for the forward reaction can easily be determined by measuring simple
quantities like a, t, xeq and x. Now, we know that the equilibrium constant for a second-order reaction
opposed by first order will be

[𝐶] (66)
𝐾=
[𝐴][𝐵]
𝑘𝑓 (67)
𝐾= 𝑏
𝑘
Now putting the value of kf from equation (65) in equation (67) and the rearranging for kb, we get

𝑥𝑒𝑞 𝑥𝑒𝑞(𝑎2−𝑥𝑒𝑞𝑥) (68)

𝑘𝑏=ln
𝑡(𝑎 −𝑥𝑒𝑞2)𝐾
2 𝑎2(𝑥𝑒𝑞−𝑥)

Hence, the value of th measuring t, xeq and x

and the equilibrium c
 Second Order
In order to second-order,
consider a general reaction in

(69)

Now, if kf ⋙kb, kb c law depending upon

both the constants ca of both the reactant A
and B; while x is the concentration of the
products after the sam on (Rf) and backward
reaction (Rb) can be g

𝑅 =𝑘 [𝐴][𝐵]=𝑘 (𝑎−𝑥)2 (70)

𝑓 𝑓 𝑓

𝑅 =𝑘 [𝐶][𝐷]=𝑘 𝑥2 (71)
𝑏 𝑏 𝑏

The net reaction rate i.e. rate of formation of the product can be given as

𝑑𝑥 (72)
=𝑘𝑓(𝑎−𝑥)2−𝑘𝑏𝑥2
𝑑𝑡
However, when the equilibrium is attained, the rate of forward reaction will be equal to the rate of backward
reaction i.e. Rf = Rb. Therefore, the equation (72) will take the form
2 2
𝑘𝑓(𝑎−𝑥𝑒𝑞) =𝑘𝑏𝑥𝑒𝑞 (73)
Where xeq is the concentration of the product C and D or the decrease in the concentration of reacant A or B at
equilibrium. Now putting the value of kb from equation (73) into equation (72), we get
2
𝑑𝑥 𝑘(𝑎−
𝑓𝑒𝑞 𝑥 ) (74)
() 22
𝑑𝑡 =𝑘𝑓 𝑎−𝑥 −
𝑥2
𝑥
𝑒 𝑞

2
𝑑𝑥 ()
𝑎− 𝑒𝑞
(75)
() 22
𝑑𝑡 =𝑘𝑓[𝑎−𝑥 − 𝑥2𝑥 𝑥]
𝑒 𝑞

or
2 (76)
𝑑𝑥 (𝑎−𝑥)2𝑥𝑒𝑞2−(𝑎−𝑥𝑒𝑞) 𝑥2
=𝑘 𝑓 []
𝑑𝑡 𝑥2𝑒𝑞

(78)

or

(80)

Integrating equation (

(81)

Using equation (81), by measuring simple

quantities like a, t, xeq rder reaction opposed
by second-order will

[𝐶][𝐷] (82)
𝐾=
[𝐴][𝐵]
𝑘𝑓 (83)
𝐾= 𝑏
𝑘
Now putting the value of kf from equation (81) in equation (83) and the rearranging for kb, we get

𝑥𝑒𝑞 𝑥(𝑎−2𝑥𝑒𝑞)+𝑎𝑥𝑒𝑞 (84)

𝑘𝑏=ln
2𝑎𝑡(𝑎−𝑥𝑒𝑞)𝐾 𝑎(𝑥𝑒𝑞−𝑥)

Hence, the value of the rate constant for backward reaction can also be obtained just by measuring t, xeq and x
and the equilibrium constant from equation (84).